JP2004279600A - Electrostatic charge image developing toner, and evaluation method and development method for the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner which excels in fluidity and transferability, forms a high image quality with good dot reproducibility and is safe to the human body, and to provide an evaluation method for the toner, a development method using the toner, a toner cartridge packed with the toner and a manufacturing and evaluation apparatus for the toner. <P>SOLUTION: The electrostatic charge image developing toner is prepared by depositing or fastening an additive to the surface of a parent toner composed of at least pigment using a metal oxide and resin and is 0.1 to1.9 mNm in the value of the torque generated when a conical rotor, kept rotated, is invaded 20 mm into a powder phase at an invasion speed 5 mm/min after the above powder is previously put into a consolidation state, and is 0.01 to 0.37 N in the value of the load generated when the conical rotor is invaded 20 mm into the powder phase. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００１７】
上式においては、１≦Ｘ＜２の条件を満たすことが好ましい。ＡがＴｉである場合の作製法を以下に示す。
Ｔｉ酸化物、Ｆｅ酸化物を秤量し、ボールミルを用いて混合する。次に電気炉等により６００〜１０００℃で２〜５時間仮焼し、その仮焼物をボールミルに投入し、粉砕した。得られた粉末を粉末プレス機にて圧力成形して板状にし、この成形物を電気炉等にて１１００〜１３００℃で２〜５時間焼成する。この焼成物をカッターで切断し、租粉砕、微粉砕し、分級機により所定の粒度に分級して、Ｔｉ酸化物とＦｅ酸化物からなる金属酸化物の粒子を得る。
Ｔｉ酸化物とＦｅ酸化物からなる金属酸化物粒子の平均粒径は０．０１〜０．２μｍが好ましい。Ｔｉ酸化物とＦｅ酸化物からなる金属酸化物粒子の平均粒径が０．０１μｍより小さい場合には凝集等が生じやすく適しておらず、０．２μｍより大きい場合には着色力が低下して適していない。
【００１８】
Ｆｅ酸化物及びＧｄ酸化物からなる金属酸化物の場合には下記組成からなる。
Ｇｄ_ｘＦｅ_３−ｘＯ_４
（式中、０．２５≦ｘ≦２であることが好ましい。）
Ｇｄ組成が０．５より少ない場合には、強い磁気特性を持つようになり、粒子同士が凝集しやすくなり、高画質には適していない。Ｇｄ組成が２より大きくなるとスピネル構造がこわれ、安定した材料が得られなくなる。
【００１９】
上記金属酸化物において、Ｇｄ組成に応じて磁気特性が変化するため、１成分用の磁性トナーから１成分、２成分用の非磁性トナーの両方の作製が可能である。Ｇｄ組成が増えるにつれて磁気特性は低下し、強磁性から非磁性に変化する（Ｇｄ組成に対する磁気特性の変化は実施例の中で示す。）。磁性トナーとして用いる場合にはＧｄ組成ｘが０．２５≦ｘ＜０．５である必要がある。非磁性トナーとして用いる場合には、０．５≦ｘ≦２である必要がある。
【００２０】
Ｇｄ酸化物とＦｅ酸化物からなる金属酸化物の作製法としては、以下のような方法などがある。
Ｇｄ酸化物、Ｆｅ酸化物を秤量し、ボールミルを用いて混合する。次に電気炉等により６００〜１０００℃で２〜５時間仮焼し、その仮焼物をボールミルに投入し、粉砕した。得られた粉末を粉末プレス機にて圧力成形して板状にし、この成形物を電気炉等にて１１００〜１３００℃で２〜５時間焼成する。この焼成物をカッターで切断し、租粉砕、微粉砕し、分級機により所定の粒度に分級して、Ｇｄ酸化物とＦｅ酸化物からなる金属酸化物の粒子を得る。
【００２１】
Ｇｄ酸化物とＦｅ酸化物からなる金属酸化物粒子の平均粒径は０．０１〜０．２μｍが好ましい。Ｇｄ酸化物とＦｅ酸化物からなる金属酸化物粒子の平均粒径が０．０１μｍより小さい場合には凝集等が生じやすく適しておらず、０．２μｍより大きい場合には着色力が低下して適していない。
【００２２】
Ｇｄ酸化物は安定した材料であり、人体にも安全であることがわかっており、医療用に用いられたりしている。そのため、Ｇｄ酸化物とＦｅ酸化物からなる金属酸化物は全く人体には安全な材料である。
【００２３】
また、これらの材料に第３添加物を添加しても良い。
例えば本発明において、下式において添加物ＢがＭｇ、Ａｌ、Ｓｉ、Ｔｉ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｇａであることを特徴とする静電荷像現像用トナーが提供される。
Ｇｄ_ｘ（Ｆｅ_１−ｙＢ_ｙ）_３−ｘＯ_４
（式中、０．２５≦ｘ≦２，０≦ｙ≦０．５である。）
【００２４】
第３の添加物Ｂは、磁気特性が強すぎる場合に添加したり、耐久性を補強する場合などに添加したりする。添加剤量は、上式中のｙ量に相当する。添加量を多くすると分離相が出来たりして、構造的に安定な材料を作製することが難しくなる。そのため、添加量ｙは０．５以下にすることが好ましい。
【００２５】
また、本発明では金属酸化物に従来から使用されている黒顔料を混合して使用することも可能である。黒顔料としては、カーボンブラック、オイルファーネスブラック、チャンネルブラック、ランプブラック、アセチレンブラック、アニリンブラック等のアジン系色素、金属塩アゾ色素、金属酸化物、金属複合酸化物がある。
【００２６】
本金属酸化物を用いてトナーを作製する場合には、樹脂１００重量部に対してＴｉ酸化物とＦｅ酸化物等からなる金属酸化物の含有量を２０〜１００重量部にすることが好ましい。２０重量部より少ない場合には画像濃度が低下し、画像のシャープ性も低下する。逆に１００重量部より多くなると、定着特性が低下し、トナー飛散などの耐久特性が低下する。
【００２７】
このように金属酸化物を顔料として用いる場合には、材料そのものの比重も異なるし、含有量的にも異なるので、トナー粒子としての流動性も新たな最適化が必要となり、本発明において、高画質化に必要なトナー流動性を規定した。
【００２８】
樹脂は、結晶性ポリエステルを用いても良い。結晶性を有し、分子量分布がシャープでかつその低分子量分の絶対量を可能な限り多くした脂肪族系ポリエステルが好ましい。この樹脂はガラス転移温度（Ｔｇ）において結晶転移を起こすと同時に、固体状態から急激に溶融粘度が低下し、紙への定着機能を発現する。この結晶性ポリエステル樹脂の使用により、樹脂のＴｇや分子量を下げ過ぎることなく低温定着化を達成することができる。そのため、Ｔｇ低下に伴なう保存性の低下はない。また、低分子量化に伴なう高すぎる光沢や耐オフセット性の悪化もない。したがってこの結晶性ポリエステル樹脂の導入は、トナーの低温定着性の向上に非常に有効である。
【００２９】
本発明において、脂肪族系の結晶性ポリエステルとしては、下記一般式（１）で表されるものが好ましい。
［−Ｏ−ＣＯ−ＣＲ_１＝ＣＲ_２−ＣＯ−Ｏ−（ＣＨ_２）_ｎ−］_ｍ （１）
（式中、Ｒ_１、Ｒ_２は炭化水素基、ｎ、ｍは繰り返し単位の数を表す。）
【００３０】
本発明のトナーおいて、低温定着性を発現し、耐ホットオフセット性を確保するためには、トナー中の樹脂および離型剤の合計量に対して、結晶性ポリエステルの含有量は１〜５０重量％が好ましく、離型剤の含有量は２〜１５重量％であることが好ましい。結晶性ポリエステルの含有量が１重量％未満の場合は低温定着性に効果がなく、５０重量％を超える場合はホットオフセット性が悪化する。離型剤含有量が２重量％未満の場合は、耐オフセット性に効果がない場合があり、１５重量％を超える場合には、トナー流動性の低下が生じる。
【００３１】
その他の樹脂としては従来からカラートナーに用いられているポリエステル樹脂または／およびポリオール樹脂等がある。ポリエステル樹脂やポリオール樹脂は、従来多用されてきたスチレン−アクリル系樹脂よりも低温定着性に優れ、耐熱保存性も比較的良いため適している。しかし、ポリエステル樹脂やポリオール樹脂は、スチレン−アクリル系樹脂に比べると、離型剤の分散性が悪い。分散性が悪いと、粉砕時に樹脂とワックスの界面に粉砕応力が集中し易いため、樹脂と離型剤の界面で粉砕され易く、粉砕されたトナーの表面には添加した離型剤の割合以上に離型剤が露出して、トナーの流動性を悪くしていた。
そこで本発明のトナーは、トナー流動性に問題のない最適な条件に入るように規定することにより、高画質化を実現できた。
【００３２】
本発明の静電荷像現像用トナーの評価法は、粉体相中に円錐ロータを回転させながら、侵入（下降）させたり、引抜（アップ）いたりさせ、そのときに円錐ロータやトナー粉体相が入っている容器にかかるトルクや荷重を測定し、そのトルクや荷重の値により流動性を評価するものである。円錐ロータの形状はどんなものでも良いが、円錐の頂角が２０〜１５０°であるものが適している。円錐の頂角が２０°より小さいとトナー粉体相との抵抗が小さいため、トルクや荷重が小さく、細かい流動性の違いを評価できない。逆に、頂角が１５０°より大きい場合には、トナー粉体相を押さえつける方向の力が大きくなり、トナー粒子の変形が生じやすくなり、トナー流動性の評価には適していない。円錐ロータの長さは、トナー粉体相の中に円錐ロータ表面が連続的に存在するような、十分な長さが必要である。
【００３３】
また、円錐ロータ表面には溝が切ってある方が良い。円錐ロータの材質面とトナー粒子との摩擦成分を測定するのではなく、トナー粒子とトナー粒子との摩擦成分を測定する方が良い。そのためには、円錐ロータが回転しながらトナー粉体相の中に侵入していくとき、円錐ロータ表面に切ってある溝の中にトナー粒子が入り込んできて、その入り込んだトナー粒子と周りのトナー粒子との摩擦状態を測定するようにした方が適している。この溝の形状は問わないが、円錐ロータの材質面とトナー粒子との接触が小さくなるように工夫する必要がある。一例を図２に示す。これは、円錐の頂点からまっすぐ底辺方向に溝を切ったもので、その溝の断面が三角形の凹凸からなるのこぎり歯形状をしている。この場合、円錐ロータ材質面とトナー粒子との接触は、三角溝の山の先端部分のみとなる。ほとんどが溝に入り込んだトナー粒子とその周辺のトナー粒子との接触となる。円錐ロータの材質は何でも良いが、加工しやすくて、表面が固く、変質しない材質が良い。また、帯電性を帯びない材質が適している。この一例としては、ＳＵＳ（ステンレス）、Ａｌ、Ｃｕ、Ａｕ、Ａｇ、黄銅等がある。
【００３４】
トナー粉体のトルクおよび荷重は、円錐ロータの回転数や円錐ロータの侵入速度により変化する。本発明の評価方法では測定の精度を上げるために、トナー粒子同士の微妙な接触状態が測定出来るように、円錐ロータの回転数や侵入速度を下げて測定するようにした。そのため、測定条件は以下に示すものである。
・円錐ロータの回転数：０．１〜１００ｒｐｍ
・円錐ロータの侵入速度：０．５〜１５０ｍｍ／ｍｉｎ
【００３５】
円錐ロータの回転数が０．１ｒｐｍより小さい場合はトナー粉体相の微妙な状態の影響を受けやすいため、トルク測定バラツキの問題が生じ、測定には適していない。１００ｒｐｍより大きい場合はトナーの飛び散り等が生じて、安定に測定できないので適していない。円錐ロータの侵入速度が０．５ｍｍ／ｍｉｎより遅い場合はトナー粉体相の微妙な状態の影響を受けやすく、測定バラツキの問題が生じるため測定には適していない。１５０ｍｍ／ｍｉｎより速い場合はトナー粉体相が圧密状態になりやすく、トナー変形等の影響が出てくるので、流動性評価には適していない。
【００３６】
本発明の評価装置構成は例えば図１に示すものであり、円錐ロータをシャフトの先端に取付け、トルクメータに固定する。そのトルクメータを昇降機により上下できるようにして、ステージの中央部にトナーを入れた容器を置くようにし、円錐ロータを下げることにより、容器の中央に円錐ロータが回転しながら侵入してくるようにする。円錐ロータにかかるトルクは上部にあるトルクメータにより検出し、トナーの入った容器にかかる荷重は容器の下にあるロードセルで検出する。円錐ロータの移動量は位置検出器で行なう。この構成は一例であり、トナーの入った容器を昇降機により上下させたりするなど他の構成でも良い。
【００３７】
円錐ロータの形は、前述したように頂角が２０〜１５０°のものが良い（図２参照）。円錐ロータの長さは、円錐ロータ部分が十分トナー相の内部まで入るように長くする必要がある。溝の形状は、どのような形状でも良いが、円錐ロータを交換したためにトルクや荷重の値が再現しなくなるということがないように注意しないといけない。そのためには、円錐ロータの溝形状は単純で、同じ形状のロータが何度でも造れる形の方が良い（図３参照）。容器の材質については問わないが、粉体との帯電による影響が出ないように導電性の材質が適している。また、粉体を入れ替えながら測定するため、汚れを少なくするために表面が鏡面に近いものが良い。容器のサイズは重要であり、円錐ロータが回転しながら侵入するときに容器の壁の影響がでないように円錐ロータの直径に対して大き目のサイズ（直径）を選択する必要がある。
【００３８】
トルクメータは高感度タイプのものが良く、非接触方式のものが適している。ロードセルは荷重レンジが広く、分解能の高いものが適している。位置検出器はリニアスケール、光を用いた変位センサ等があるが、精度的に０．１ｍｍ以下の仕様が適している。昇降機は、サーボモータやステッピングモータを用いて、精度良く駆動できるものが良い。
【００３９】
測定は、容器にトナーを一定量投入し、本装置にセットする。その後、円錐ロータを回転させながらトナー粉体相の中に侵入させる。しかし、実際の測定には円錘ロータを侵入させる前に、トナー粉体相を加圧して、圧密状態を作り出し、その圧密状態のトナー相に円錐ロータを下降させ測定を行なう。トルクや荷重測定に入るときには、決められた回転数、侵入速度で行なう。円錐ロータの回転方向は任意である。円錐ロータの侵入距離は、浅いとトルクや荷重の値が小さく、データの再現性等に問題が生じるため、データの再現性のある領域まで深く円錐ロータを侵入させた方が良い。我々の実験結果では５ｍｍ以上侵入させればほぼ安定した測定が可能になった。
【００４０】
測定モードは、どのような条件でも可能であるが、例として以下のような測定モードがある。
▲１▼ 容器にトナーを充填する。
▲２▼ トナー粉体相を加圧して、圧密状態作り出す。
▲３▼ 円錐ロータを回転させながら侵入させ、そのときのトルク、荷重を測定する。
▲４▼ 円錐ロータがトナー表面層から予め設定した深さ迄侵入したところで、侵入動作を止める。
▲５▼ 円錐ロータを引抜く動作を開始する。
▲６▼ 円錐ロータの先端がトナー粉体相表面から抜け、完全にフリーになった時点（最初のホームポジション）で円錐ロータの引抜き動作を停止し、回転も止める。
以上の▲１▼〜▲６▼の操作を繰返して、測定を行なう。連続的に行なっても良い。
【００４１】
また、別の測定法としては、トナー粉体相を測定前に加振器により振動を与えて安定化させ、その安定化したトナー粉体相を加圧し圧密状態にし、圧密状態のトナー粉体相に回転させながら円錐ロータを侵入させ、そのときのトルクや荷重を測定し、予め設定した深さ迄到達したら侵入動作を止め、その後円錐ロータを最初の位置（ホームポジション）迄アップさせる。
さらにまた、別な測定法としては、圧密状態のトナー粉体相に、円錐ロータを侵入させて、予め設定したトルク値になるまでの深さを調べる方法等がある。
【００４２】
本発明における測定法では、トナー粉体相の空間率が重要になるが、我々の実験結果では空間率は０．５以上のとき安定して測定が可能であった。０．５未満では圧密状態の作製に時間がかかり、連続的な測定が困難であった。トナー粉体相の空間率の範囲としては、種々な測定法の場合を含めて、０．５〜０．６４であった。０．６４より大きい場合には装置等での実使用条件との対応が出来ず、測定には適していない。この空間率の変化は、トナー粉体相に荷重を加えるなどして加圧し、作り出す。
【００４３】
本発明において、圧密状態とは、解放された状態ではなく、容器などの閉ざされた状態に粉体が充填され、種々の方法により再配列された状態をいう。
また、トナー粉体相の空間率とは、粉体相内に存在する隙間の割合を示すものであり、下記式により求められる。
空間率＝（嵩体積−真体積）／真体積
しかし、測定系、測定条件等に関してはこの限りではない。
【００４４】
本発明のトナーは、高画質画像を実現するために、トナーの体積平均粒径が４〜１０μｍであることが好ましい。さらに好ましくは４〜７μｍである。体積平均粒径４μｍ未満では長期間の使用でのトナー飛散による機内の汚れ、低湿環境下での画像濃度低下、感光体クリーニング不良等という問題が生じやすく、人体への影響も懸念される。また体積平均粒径が１０μｍを超える場合では１００μｍ以下の微小スポットの解像度が充分でなく非画像部への飛び散りも多く画像品位が劣る傾向となる。
【００４５】
本発明のトナーを用いる現像剤は、高画質画像を実現するために、キャリアの平均粒径が２０〜１００μｍであることが好ましい。キャリアの平均粒径が２０〜１００μｍの範囲にあると、現像機内部のトナー濃度が２〜１０重量％の範囲内において、トナーの帯電量をより均一にすることができる。２０μｍより小さくなるとキャリア粒子の感光体上への付着等が生じやすく、さらにトナーとの撹拌効率が悪くなりトナーの均一な帯電量が得られにくくなる。逆に、キャリアの平均粒径が１００μｍを超える場合では、細かい画像再現性が悪くなり、高画質は得られない。
トナーおよび現像剤の詳細を以下に示す。
【００４６】
樹脂としては、脂肪族系の結晶性ポリエステルを含有することが好ましく、結晶性ポリエステル樹脂の分子構造については、限定的でないが、ポリエステル樹脂の結晶性および軟化点の観点から、炭素数２〜６のジオール化合物、特に１，４−ブタンジオール、１，６−ヘキサンジオールおよびこれらの誘導体を含有するアルコール成分と、マレイン酸、フマル酸、コハク酸、およびこれらの誘導体を含有する酸成分とを用いて合成される下記一般式（１）で表される脂肪族系ポリエステルを含有することが好ましい。
［−Ｏ−ＣＯ−ＣＲ_１＝ＣＲ_２−ＣＯ−Ｏ−（ＣＨ_２）_ｎ−］_ｍ （１）
（式中、Ｒ_１、Ｒ_２は炭化水素基、ｎ、ｍは繰り返し単位の数である。）
また、ポリエステル樹脂の結晶性および軟化点の観点から、非線状のポリエステルを合成するためにアルコール成分にグリセリン等の３価以上の多価アルコールを追加し、酸成分に無水トリメリット酸などの３価以上の多価カルボン酸を追加して縮重合を行っても良い。
【００４７】
結晶性ポリエステル樹脂のガラス転移温度（Ｔｇ）は耐熱保存性が悪化しない範囲で低いことが望ましく、８０〜１３０℃の範囲にあることが好ましい。
ガラス転移温度（Ｔｇ）が８０℃以下の場合は耐熱保存性が悪化し、現像装置内部の温度でブロッキングが発生しやすくなり、１３０℃の場合には定着下限温度が高くなるため低温定着性が得られなくなる。結晶性ポリエステル樹脂のガラス転移温度（Ｔｇ）は、ＤＳＣによる２ｎｄ昇温時の吸熱ピーク温度である。
【００４８】
また樹脂としては、前記一般式（１）で表される脂肪族系の結晶性ポリエステル以外にも、従来からトナー用樹脂として用いられているものを全て用いることができ、例えばポリスチレン樹脂、エポキシ樹脂、ポリエステル樹脂、ポリアミド樹脂、スチレン−アクリル樹脂、スチレン−メタクリレート樹脂、ポリウレタン樹脂、ビニル樹脂、ポリオレフィン樹脂、スチレンブタジエン樹脂、フェノール樹脂、ポリエチレン樹脂、シリコン樹脂、ブチラール樹脂、テルペン樹脂、ポリオール樹脂等がある。
【００４９】
ビニル樹脂としては、ポリスチレン、ポリ−ｐ−クロロスチレン、ポリビニルトルエンなどのスチレン及びその置換体の単重合体：スチレン−ｐ−クロロスチレン共重合体、スチレン−プロピレン共重合体、スチレン−ビニルトルエン共重合体、スチレン−ビニルナフタリン共重合体、スチレン−アクリル酸メチル共重合体、スチレン−アクリル酸エチル共重合体、スチレン−アクリル酸ブチル共重合体、スチレン−アクリル酸オクチル共重合体、スチレン−メタクリル酸メチル共重合体、スチレン−メタクリル酸エチル共重合体、スチレン−メタクリル酸ブチル共重合体、スチレン−α−クロロメタクリル酸メチル共重合体、スチレン−アクリロニトリル共重合体、スチレン−ビニルメチルエーテル共重合体、スチレン−ビニルエチルエーテル共重合体、スチレン−ビニルメチルケトン共重合体、スチレン−ブタジエン共重合体、スチレン−イソプレン共重合体、スチレン−アクリロニトリル−インデン共重合体、スチレン−マレイン酸共重合体、スチレン−マレイン酸エステル共重合体などのスチレン系共重合体：ポリメチルメタクリレート、ポリブチルメタクリレート、ポリ塩化ビニル、ポリ酢酸ビニル等がある。
【００５０】
ポリエステル樹脂としては以下のＡ群に示したような２価のアルコール成分と、Ｂ群に示したような二塩基酸成分からなるものであり、さらにＣ群に示したような３価以上のアルコールあるいはカルボン酸を第三成分として加えてもよい。
【００５１】
Ａ群：エチレングリコール、トリエチレングリコール、１，２−プロピレングリコール、１，３−プロピレングリコール、１，４−ブタンジオール、ネオペンチルグリコール、１，４−ブテンジオール、１，４−ビス（ヒドロキシメチル）シクロヘキサン、ビスフェノールＡ、水素添加ビスフェノールＡ、ポリオキシエチレン化ビスフェノールＡ、ポリオキシプロピレン（２，２）−２，２’−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン（３，３）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシエチレン（２，０）−２，２−ビス（４−ヒドロキシフェニル）プロパン、ポリオキシプロピレン（２，０）−２，２’−ビス（４−ヒドロキシフェニル）プロパン等。
【００５２】
Ｂ群：マレイン酸、フマール酸、メサコニン酸、シトラコン酸、イタコン酸、グルタコン酸、フタール酸、イソフタール酸、テレフタール酸、シクロヘキサンジカルボン酸、コハク酸、アジピン酸、セバチン酸、マロン酸、リノレイン酸、またはこれらの酸無水物または低級アルコールのエステル等。
【００５３】
Ｃ群：グリセリン、トリメチロールプロパン、ペンタエリスリトール等の３価以上のアルコール、トリメリト酸、ピロメリト酸等の３価以上のカルボン酸等。
【００５４】
ポリオール樹脂としては、エポキシ樹脂と２価フェノールのアルキレンオキサイド付加物、もしくはそのグリシジルエーテルとエポキシ基と反応する活性水素を分子中に１個有する化合物と、エポキシ樹脂と反応する活性水素を分子中に２個以上有する化合物を反応してなるものなどがある。
【００５５】
本発明で用いる顔料としては前述した金属酸化物を用いる。
トナーにおいては、良好な顔料の均一分散が必須となり、顔料を直接大量の樹脂中に投入するのではなく、一度高濃度に顔料を分散させたマスターバッチを作製し、それを希釈する形で投入する方式が用いられている。この場合、一般的には、分散性を助けるために溶剤が使用されていたが、環境等の問題があり、本発明では水を使用して分散させた。水を使用する場合、マスターバッチ中の残水分が問題にならないように、温度コントロールが重要になる。
【００５６】
本発明のトナーには電荷制御剤をトナー粒子内部に配合（内添）することが好ましい。しかし、トナー粒子と混合（外添）して用いても良い。電荷制御剤によって、現像システムに応じた最適の電荷量コントロールが可能となり、特に本発明では、粒度分布と電荷量とのバランスを更に安定したものとすることが可能である。
【００５７】
トナーを正電荷性に制御するものとして、ニグロシンおよび四級アンモニウム塩、トリフェニルメタン系染料、イミダゾール金属錯体や塩類を、単独あるいは２種類以上組み合わせて用いることができる。また、トナーを負電荷性に制御するものとしてサリチル酸金属錯体や塩類、有機ホウ素塩類、カリックスアレン系化合物等が用いられる。
【００５８】
また、本発明におけるトナーには定着時のオフセット防止のために離型剤を内添することが可能である。離型剤としては、キャンデリラワックス、カルナウバワックス、ライスワックスなどの天然ワックス、モンタンワックスおよびその誘導体、パラフィンワックスおよびその誘導体、ポリオレフィンワックスおよびその誘導体、サゾールワックス、低分子量ポリエチレン、低分子量ポリプロピレン、アルキルリン酸エステル等がある。これら離型剤の融点は６５〜９０℃であることが好ましい。この範囲より低い場合には、トナーの保存時のブロッキングが発生しやすくなり、この範囲より高い場合には定着ローラー温度が低い領域でオフセットが発生しやすくなる場合がある。
【００５９】
離型剤等の分散性を向上させるなどの目的の為に、添加剤を加えても良い。添加剤としては、スチレン−アクリル樹脂、ポリエチレン樹脂、ポリスチレン樹脂、エポキシ樹脂、ポリエステル樹脂、ポリアミド樹脂、スチレン−メタクリレート樹脂、ポリウレタン樹脂、ビニル樹脂、ポリオレフィン樹脂、スチレン−ブタジエン樹脂、フェノール樹脂、ブチラール樹脂、テルペン樹脂、ポリオール樹脂等があり、それぞれの樹脂を２種以上混合した物でも良い。
【００６０】
また、本トナーに粉砕性を向上させるために粉砕助剤を含ませても良い。本材料としては、ビニルトルエン、α−メチルスチレンおよびイソプロペニルトルエンからなる群から選ばれる少なくとも１種のモノマーの重合体を含む樹脂等である。本重合体はビニルトルエン、α−メチルスチレンまたはイソプロペニルトルエンの単独重合体であってもよいし、これらのモノマー同志の共重合体であってもよい。これらの重合体にはスチレン以外の他のモノマーが共重合されていないのが好ましいが、本発明の目的を損なわない範囲でスチレン以外の他のモノマーが共重合されていてもよい。
【００６１】
スチレンの含有量は共重合体を構成する全モノマーに占めるスチレンの割合として５０モル％以下、好ましくは２０〜４０モル％であることが望ましい。これらの樹脂は脆いために、結晶性ポリエステルと組み合わせて使用すると、結晶性ポリエステルの結晶性に起因する不十分な粉砕性を向上させることが出来る。
【００６２】
また、磁性トナーとする場合には、トナー粒子の中に磁性体の微粒子を内添すれば良い。磁性体としては、フェライト、マグネタイト、鉄、ニッケル、コバルト、それらの合金などの強磁性体等が考えられる。磁性体の平均粒径は０．１〜１μｍが好ましい。磁性体の含有量はトナー１００重量部に対して、１０から７０重量部であることが好ましい。
【００６３】
また、前述したように本発明のトナーは流動性向上剤として無機微粉体をトナー表面に付着または固着させる。この無機微粉体の平均粒径は１０〜２００ｎｍが適している。１０ｎｍより小さい粒径の場合には流動性に効果のある凹凸表面を作り出すことが難しく、２００ｎｍより大きい粒径の場合には粉体形状がラフになり、トナー形状の問題が生じる。
【００６４】
本発明の無機微粉体としてはＳｉ、Ｔｉ、Ａｌ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｉｎ、Ｇａ、Ｎｉ、Ｍｎ、Ｗ、Ｆｅ、Ｃｏ、Ｚｎ、Ｃｒ、Ｍｏ、Ｃｕ、Ａｇ、Ｖ、Ｚｒ等の酸化物や複合酸化物が挙げられる。これらのうち二酸化珪素（シリカ）、二酸化チタン（チタニア）、アルミナの微粒子が好適に用いられる。
【００６５】
さらに、疎水化処理剤等により表面改質処理することが有効である。疎水化処理剤の代表例としては以下のものが挙げられる。
ジメチルジクロルシラン、トリメチルクロルシラン、メチルトリクロルシラン、アリルジメチルジクロルシラン、アリルフェニルジクロルシラン、ベンジルジメチルクロルシラン、ブロムメチルジメチルクロルシラン、α−クロルエチルトリクロルシラン、ｐ−クロルエチルトリクロルシラン、クロルメチルジメチルクロルシラン、クロルメチルトリクロルシラン、ヘキサフェニルジシラザン、ヘキサトリルジシラザン等。
【００６６】
無機微粉体はトナーに対して０．１〜２重量％使用されるのが好ましい。０．１重量％未満では、トナー凝集を改善する効果が乏しくなり、２重量％を超える場合は、細線間のトナー飛び散り、機内の汚染、感光体の傷や摩耗等の問題が生じやすい傾向がある。
【００６７】
また、少なくとも樹脂、顔料からなる粉体の表面に電荷制御剤を付着または固着させ、粉体表面形状を小さな周期と大きな周期を持つようにしても良い。その平均粒径は１０〜２００ｎｍの小さい粒径のものが最適である。１０ｎｍより小さい粒径の場合には流動性に効果のある凹凸表面を作り出すことが難しく、２００ｎｍより大きい粒径の場合には粉体形状がラフになり、トナー形状の問題が生じる。電荷制御剤としては、ニグロシンおよび四級アンモニウム塩、トリフェニルメタン系染料、イミダゾール金属錯体や塩類、サリチル酸金属錯体や塩類、有機ホウ素塩類、カリックスアレン系化合物等があり、２種類以上組み合わせたりしても良い。
【００６８】
また、本発明のトナーには、実質的な悪影響を与えない範囲内で更に他の添加剤、例えばテフロン（Ｒ）粉末、ステアリン酸亜鉛粉末、ポリフッ化ビニリデン粉末の如き滑剤粉末；あるいは酸化セリウム粉末、炭化珪素粉末、チタン酸ストロンチウム粉末などの研磨剤；あるいは例えばカーボンブラック粉末、酸化亜鉛粉末、酸化スズ粉末等の導電性付与剤を現像性向上剤として少量用いることもできる。
【００６９】
本発明に係るトナーを作製する方法としては、粉砕法、重合法（懸濁重合、乳化重合分散重合、乳化凝集、乳化会合等）等があるが、これらの作製法に限るものではない。
【００７０】
粉砕法の一例としては、まず、前述した樹脂、着色剤としての顔料または染料、電荷制御剤、離型剤、その他の添加剤等をヘンシェルミキサーの如き混合機により充分に混合した後、バッチ式の２本ロール、バンバリーミキサーや連続式の２軸押出し機、連続式の１軸混練機等の熱混練機を用いて構成材料をよく混練し、圧延冷却後、切断を行なう。切断後のトナー混練物は破砕を行ない、ハンマーミル等を用いて粗粉砕し、更にジェット気流を用いた微粉砕機や機械式粉砕機により微粉砕し、旋回気流を用いた分級機やコアンダ効果を用いた分級機により所定の粒度に分級する。その後、混合機により無機粒子などからなる添加剤を粒子表面に付着もしくは固着させる。この混合工程後のトナー粒子の流動性を本評価法を用いて評価する。この場合、抜き取り検査で、試料を試料容器に入れ、加圧等により圧密状態にし、その試料容器を直接図１に示す評価装置の試料台に載せ測定を行なう。円錐ロータの回転数は０．１〜１０ｒｐｍとし、円錐ロータの侵入速度は５ｍｍ／ｍｉｎとした。測定は、円錐ロータを回転させながら侵入させ、５ｍｍ以上の予め設定した侵入距離を経た後は侵入を止め、その後円錐ロータを引抜き、元の初期位置に戻す。この円錐ロータのトナー粉体相への侵入時のトルク、荷重を測定し、トナーの流動性を評価する。
【００７１】
本発明の評価法でトナー流動性を評価した場合には、測定値（トルク、荷重）とトナー流動性が以下のような関係になる。
トルクが小さい場合、流動性は良い。
トルクが大きい場合、流動性は悪い。
荷重が小さい場合、流動性は良い。
荷重が大きい場合、流動性は悪い。
【００７２】
円錐ロータを用いた本発明の評価法の特徴は、以下のようになり、抜取り試料をそのまま迅速に、簡単に測定できるため、個人差の無い、精度の高い測定が出来ることにある。
▲１▼ 非破壊検査である。
▲２▼ 試料をそのまま測定できる。
▲３▼ 短時間で測定できる。
▲４▼ 誰にでも簡単に測定できる。
そのため、製造ラインでの計測も可能であり、製造工程の中での各工程間に設置して、工程途中での品質評価ができる。例えば、混合工程を経た後、次工程へ粉体試料を搬送する途中に、試料抜取り・測定ゾーンを設けておき、あるタイミングでシャッターを開閉して、一定量の試料を測定部へ搬送する。その測定部の先端部はＳＵＳ等でできた容器になっており、そのまま本評価方法にて測定する。または、その容器を近くの別の場所にある本評価装置へ持っていき、試料ステージへのせて本評価方法にて測定する。評価の結果、その数値が予め定めた設定範囲を外れていた場合、試料を充填工程へは回さず、トナーの再処理工程へ回す。これらの仕組みは、混合工程前の工程である粉砕・分級工程後の検査、混合工程の後にある風篩工程後の検査、充填前の検査等に適用できる（図４参照）。
また、これらの機能をもったトナー評価装置を単独に開発段階の評価装置として使うことも可能である。
【００７３】
トナーの場合、前述の通り本評価法でのトルク、荷重の測定値は流動性を示しており、定量的な評価が可能となる。今までの従来の評価法では、トナー間の違いは評価出来るが、トナーの種類が違うと同じ土俵では評価できないという問題があった。しかし、本評価法で測定した値は、粉体特性としてのトルク値、荷重値であり、トナーの種類が変わっても粒径が変わっても同じ土俵で評価出来る値であり、非常に汎用的な評価値になる。
【００７４】
トナー粉体相中での円錐ロータの移動時のトルク、荷重特性は、粉体の流動性と密接な関係があり、粉体の流動性が良い場合には１個１個の粉体粒子間の付着力が小さいために動きやすく、その粉体相内で円錐ロータを動かしてもトルクは小さく、荷重変化も小さい。しかし、逆に粉体の流動性が悪い場合には、１個１個の粉体粒子間の付着力が大きいために動きにくく、その粉体相内で円錐ロータを移動した場合には円錐ロータにかかるトルクは大きくなり、下方向へ働く力（荷重）も大きくなる。特に、この現象はトナー中に離型剤等を入れた場合に微妙な変化として現れ、１個１個の粉体粒子間の付着力は圧密状態でより顕著に現れる。そのため、圧密状態でのトナー流動性を評価する必要がある。
【００７５】
よって、本発明の評価法では、以下のような関係で流動性を評価出来る。
流動性が良い場合→圧密状態の粉体相内を移動したときのトルク、荷重が小さい。
流動性が悪い場合→圧密状態の粉体相内を移動したときのトルク、荷重が大きい。
【００７６】
トナーの流動性は、トナー作製工程の中の混合工程によりほとんど決まる。つまり、無機粒子などからなる添加剤をトナー粒子表面に付着もしくは固着させる状態によって、トナー粒子の流動性は大きく変化する。
トナーの混合状態は、混合工程での混合条件（仕込み量、回転数、混合時間等）によって変化する。そのため、流動性には混合条件が重要な役割を果たし、混合工程後の流動性の評価が重要となる。
【００７７】
プリンタや複写機において、高画質化を実現するためには、非常に微小なドット再現性を高める必要がある。それを実現するためには、非常に微小な潜像に対して忠実なトナー現像が必要となる。この忠実な現像を可能にするためには、現像域に均一なトナーブラシを搬送、供給する必要がある。そのためには、トナー帯電量が適度な条件であることが必要であるが、常に安定して現像域に均一なトナーブラシが供給できるようなトナーの動き易さ、搬送のし易さが非常に重要となる。つまり、微小なドット再現性を上げるためには、トナーの流動性を上げることが必要になる。特に、離型剤を入れたトナーにおいては、圧密状態での流動性を上げる必要がある。
【００７８】
そこで、顔料に金属酸化物を用いた本発明のトナーの流動性を円錐ロータを用いた本発明の評価方法により評価し、ドット再現性及びトナー搬送性との関係を調べた結果、非常に強い相関関係が存在し、トルクや荷重が小さいときドット再現性及びトナー搬送性は良くなった。
その結果から、高画質化を可能にする金属酸化物を用いたトナーは、以下のようなトルク、荷重特性を示すことが分かった。
【００７９】
▲１▼ 円錐ロータ侵入時（２０ｍｍ侵入時）のトルクの値が０．１〜１．９ｍＮｍである。
▲２▼ 円錐ロータ侵入時（２０ｍｍ侵入時）の荷重の値が０．０１〜０．３７Ｎである。
（ここで、円錐ロータの侵入速度：５ｍｍ／ｍｉｎ、空間率：０．５０〜０．６４）
なお、評価モードに関しては、他の方法を用いても問題ない。また、評価項目もトルクや荷重以外で、ある荷重になるまでの侵入距離、あるトルクになるまでの侵入距離等であっても良いし、トルクや荷重の積分値を評価しても良い。また、他の評価項目であっても良い。
【００８０】
本発明のトナーは、混合工程後、２５０メッシュ以上の篩を通過させ、粗大粒子、凝集粒子を除去して得られたものである。
【００８１】
本発明に係るトナーを作製する方法としては、粉砕法以外の方法が考えられ、重合法の一例としては、モノマーに着色剤（顔料）及び電荷制御剤等を添加したモノマー組成物を水系の媒体中で懸濁し重合させることでトナー粒子を得る。造粒法は特に限定されない。
【００８２】
例えば本発明のトナーは、有機溶媒中に少なくとも、イソシアネート基を含有するポリエステル系プレポリマーが溶解し、顔料系着色剤が分散し、離型剤が溶解ないし分散している油性分散液を水系媒体中に無機微粒子及び／又はポリマー微粒子の存在下で分散させるとともに、この分散液中で該プレポリマーをポリアミン及び／又は活性水素含有基を有するモノアミンと反応させてウレア基を有するウレア変性ポリエステル系樹脂を形成させ、このウレア変性ポリエステル系樹脂を含む分散液からそれに含まれる液状媒体を除去することにより得られる。
ウレア変性ポリエステル系樹脂において、そのＴｇは４０〜６５℃、好ましくは４５〜６０℃である。その数平均分子量Ｍｎは２５００〜５００００、好ましくは２５００〜３００００である。その重量平均分子量Ｍｗは１万〜５０万、好ましくは３万〜１０万である。
【００８３】
このトナーは、該プレポリマーと該アミンとの反応によって高分子量化されたウレア結合を有するウレア変性ポリエステル系樹脂をバインダー樹脂として含む。そして、そのバインダー樹脂中には着色剤が高分散している。
得られた乾燥後のトナーの粉体を風力分級し、上記最適な混合条件により混合機により無機微粒子などからなる添加剤を粒子表面に付着もしくは固着させる。また、電荷制御剤を乾燥後のトナー粉体表面に打込んで、固着注入させても良い。さらにその後、無機微粒子などからかる添加剤を粒子表面に付着もしくは固着させても良い。電荷制御剤を表面に打込むことにより、トナーの帯電量の制御がしやすくなる。
【００８４】
各作製方法において、混合したり、固着注入したりする具体的手段としては、高速で回転する羽根によって粉体混合物に衝撃力を加える方法、高速気流中に粉体混合物を投入し、加速させ、粒子同士または複合化した粒子を適当な衝突板に衝突させる方法などがある。装置としては、オングミル（ホソカワミクロン社製）、Ｉ式ミル（日本ニューマチック社製）を改造して、粉砕エアー圧カを下げた装置、ハイブリダイゼイションシステム（奈良機械製作所社製）、クリプトロンシステム（川崎重工業社製）、自動乳鉢などがあげられる。
【００８５】
これらの方式の場合にも、造粒後の検査、電荷制御剤の処理後の検査、添加剤の混合工程後の検査、混合工程の後にある風篩工程後の検査、充填前の検査等に適用できる。
また、本発明の評価法は混練り工程や粉砕工程を用いないで作製する重合法やスプレードライ法などで作製したトナー、カプセルトナーにも使用できる。
【００８６】
また、トナーの流動性はトナー粒子形状によって影響されるが、トナーの平均円形度が０．９０〜０．９９である非常に球形に近いトナーの場合には流動性に優れ、ドット再現性に優れた高画質化を実現できる。
【００８７】
また、トナー粒子の円形度はフロー式粒子像分析装置ＦＰＩＡ−１０００（東亜医用電子株式会社製）により平均円形度として計算し、１に近いほど球形に近いと評価できる。
【００８８】
本発明のトナーは、接触または非接触現像方式に使用する１成分現像剤として用いる。接触または非接触現像方式は色々な公知のものが使用される。例えば、アルミスリーブを用いた接触現像法、導電性ゴムベルトを用いた接触現像法、アルミ素管の表面にカーボンブラック等を含む導電性樹脂層を形成した現像スリーブを用いる非接触現像法等がある。また、本発明のトナーを用いた現像時にＡＣバイアス電圧成分を印加すると、現像効率が向上し、画像特性が向上する。
【００８９】
また、１成分現像方式において、トナー供給部の出口にトナー層を均一にするためのローラー状のブレードを設けた現像方式に、本トナーを用いることを特徴とする。このような方式の場合には、感光体へのフィルミングだけではなく、ドクターローラへのフィルミングが発生する。このため、トナー層が均一に形成できないばかりかトナー帯電が不均一になり、トナー電荷量も小さくなる。このため現像不良が生じる。
しかし本発明のトナーを用いると、ドクターローラへのフィルミングは発生せず、安定した現像が行なわれ、耐久特性に優れた方式となる（図５参照。）。
【００９０】
本発明のトナーは流動性に優れているため、カートリッジ容器に入れて保管することが十分可能であり、カートリッジ容器から現像部へトナー搬送するような構成の装置にも適している。
【００９１】
さらに二成分現像剤として使用する場合は、磁性キャリアと所定の混合比率で混合することによって二成分現像剤とする。
【００９２】
二成分現像剤に使用されるキャリアとしては公知のものが使用可能であり、例えば鉄粉、フェライト粉、ニッケル粉、マグネタイト粉の如き磁性粒子あるいはこれら磁性粒子の表面をフッ素系樹脂、ビニル系樹脂、シリコーン系樹脂等で処理したもの、あるいは磁性粒子が樹脂中に分散されている磁性粒子分散樹脂粒子等が挙げられる。これら磁性キャリアの平均粒径は２０〜１００μｍが良い。好ましくは２０〜７０μｍが良い。
【００９３】
【実施例】
以下、実施例を説明するが、これは本発明を何ら限定するものではない。
【００９４】
（評価）
トナーの評価において、トナー組成、トナー作製法および混合条件を変化したトナーを作製し、トナー流動性を本発明の評価法を用いて評価し、画像濃度及びドット再現性を画像のザラツキ感として５段階評価（ランク１：悪い→ランク５：良い）した。
また、２万枚のランニング耐久試験を行ない、現像部でのブロッキング等のトナー搬送性の不具合点を評価した。不具合点の無かった場合を○、不具合点のあった場合を×として評価した。
トナーの流動性は、円錐ロータが侵入時のトナー粉体相表面から２０ｍｍ侵入したときのトルクと荷重の値を測定した。トナーは予め圧密状態にし、空間率を測定しトルク、荷重を評価した。円錐ロータの評価条件は以下のようにした。
・圧密荷重：２５０ｇ
・円錐ロータの頂角：５０°
・円錐ロータの回転数：１ｒｐｍ
・円錐ロータの侵入速度：５ｍｍ／ｍｉｎ
なお、以下の配合における部数は全て重量部である。
【００９５】
実施例１
樹脂：ポリエステル樹脂 １００部
顔料：（ＴｉＯ）・Ｆｅ_２Ｏ ３３０部
帯電制御剤：サルチル酸亜鉛塩 ５部
離型剤：低分子量ポリエチレン ５部
上記原材料をミキサーで十分に混合した後、２軸押出し機によりバレル温度１００℃、混練機回転数１２０ｒｐｍで溶融混練した。混練物を圧延冷却後カッターミルで粗粉砕し、ジェット気流を用いた微粉砕機で粉砕後、旋回式風力分級装置を用いて、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【００９６】
実施例２
実施例１と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【００９７】
実施例３
実施例１と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【００９８】
実施例４
実施例１と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【００９９】
比較例１
実施例１と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【０１００】

上記原材料をミキサーで十分に混合した後、２軸押出し機によりバレル温度１００℃回転数１２０ｒｐｍで溶融混練した。混練物を圧延冷却後カッターミルで粗粉砕し、ジェット気流を用いた微粉砕機で粉砕後、旋回式風力分級装置を用いて、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【０１０１】
実施例６
実施例５と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【０１０２】
実施例７
実施例５と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【０１０３】
実施例８
実施例５と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【０１０４】
比較例２
実施例５と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。
添加剤：シリカ微粉末 １．０部
混合回転数 ７００ｒｐｍ
混合時間 １２０ｓｅｃ
混合機 スーパーミキサー
本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【０１０５】
実施例９
樹脂：ポリエステル樹脂 １００部
顔料：（ＧｄＯ）・Ｆｅ_２Ｏ_３ ４０部
帯電制御剤：サルチル酸亜鉛塩 ５部
離型剤：低分子量ポリエチレン ５部
上記原材料をミキサーで十分に混合した後、２軸押出し機によりバレル温度１００℃混練機回転数１２０ｒｐｍで溶融混練した。混練物を圧延冷却後カッターミルで粗粉砕し、ジェット気流を用いた微粉砕機で粉砕後、旋回式風力分級装置を用いて、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果、表１に示す。
【０１０６】
実施例１０
実施例９と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【０１０７】
実施例１１
実施例９と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【０１０８】
比較例３
実施例９と同様の原材料、作製方法で混練、粉砕、分級を行ない、平均粒径が６．５μｍの粒度分布に分級した。
さらに、母体着色粒子１００部に対して、以下の混合条件にて添加剤を混合し、トナーを作製した。

本トナーを作製した後、本評価法により流動性を測定した。結果を表１に示す。
また、得られたトナーを潜像担持体がＯＰＣドラム感光体でクリーニング方式がブレードクリーニングである複写機にセットし、画像評価実験およびランニング実験を行なった。その結果を表１に示す。
【０１０９】
【表１】

【０１１０】
上記のデータをグラフ化して、図６、７に示す。図６は実施例１〜１１、比較例１〜３の円錐ロータ侵入時のトルクとドット再現性との関係、図７は実施例１〜１１、比較例１〜３の円錐ロータ侵入時の荷重とドット再現性との関係を示す。
【０１１１】
以上の結果から分かるように、トナー粉体相の本発明の評価法による流動性評価値と画像濃度、ドット再現性及びトナー搬送性との間には強い相関関係が存在し、本発明の評価法により画像品質、トナー搬送性を評価できることが分かる。図６、７の結果から、ドット再現性の良い高画質を得るために必要な、流動性の良いトナーを得るためには、以下の条件を満足することが必要であることが分る。
▲１▼ 円錐ロータ侵入時のトルクの値が０．１〜１．９ｍＮｍである。
▲２▼ 円錐ロータ侵入時の荷重の値が０．０１〜０．３７Ｎである。
（ここで、ロータ侵入速度：５ｍｍ／ｍｉｎ、２０ｍｍ侵入時の値）
円錐ロータ侵入時のトルク値が０．１ｍＮｍ未満では、トナーの流動性以外の帯電特性が悪くなり画質低下が生じ、１．９ｍＮｍより大きくなれば流動性が低下し、画像濃度が低下し、ドット再現性及びトナー搬送性が悪くなる。円錐ロータ侵入時の荷重値が０．０１Ｎ未満では、トナーの帯電特性が悪くなり画質低下が生じ、０．３７Ｎより大きくなるとトナーの流動性が低下し、画像濃度が低下し、ドット再現性及びトナー搬送性が悪くなる。
【０１１２】
【発明の効果】
本発明により、少なくとも金属酸化物を用いた顔料及び樹脂からなる母体トナー粉体の流動性を、この粉体を予め圧密状態にした後、粉体相中に円錐ロータを回転させながら侵入させ、円錐ロータが粉体相中を侵入したときに発生するトルクまたは荷重を規定することにより、トナー搬送性が良く、画像濃度が高く、ドット再現性の良い高画質の得られる人体にやさしい静電荷像現像用トナーを安定して提供することができる。
また、本発明により、上記トナーの評価方法、該トナーを用いる現像方法、該トナーを充填したトナーカートリッジ、該トナーの製造方法及び評価装置を提供することができる。
【図面の簡単な説明】
【図１】本発明の評価装置構成の概要図である。
【図２】（ａ）は円錐ロータの形状の一例を示す図である。
（ｂ）は（ａ）の断面図である。
【図３】（ａ）は円錐ローラの上から見た図である。
（ｂ）は円錐ローラの別の例の上から見た図である。
（ｃ）は円錐ロータの横から見た図である。
【図４】本発明の評価装置を備えたトナー製造装置の概略図である。
【図５】本発明の静電荷像現像用トナーを用いた現像装置の概略図である。
【図６】実施例１〜１１及び比較例１〜３の円錘ロータ侵入時のトルクとドット再現性との関係を示す図である。
【図７】実施例１〜１１及び比較例１〜３の円錘ロータ侵入時の荷重とドット再現性との関係を示す図である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a toner for developing an electrostatic image used in a one-component development method or a two-component development method, a method for evaluating the toner, a development method using the toner, a toner cartridge filled with the toner, a method for manufacturing the toner, and evaluation. Equipment related.
[0002]
[Prior art]
As a method for evaluating the fluidity of an electrophotographic toner or the like, Japanese Patent Application Laid-Open No. 01-203941 (Patent Document 1) of Hitachi Chemical Co., Ltd. discloses a method of dropping through a narrow portion of a funnel to which a magnetic field is applied. A method for accurately evaluating the fluidity of a developer in a developing machine by measuring the time required for the development has been proposed. Japanese Patent Application Laid-Open No. 04-116449 of Fujitsu (Patent Literature 2) puts toner on a tiltable plate, gradually tilts the plate, and measures the angle when the flow starts and when the flow ends. A method has been proposed. Further, Sharp's Japanese Patent Application Laid-Open No. 2000-292967 (Patent Literature 3) discloses a method in which a sieve is stacked in several stages, toner is poured on the sieve, and horizontal and vertical vibrations are applied to the sieve portion for a certain period of time. A method has been proposed in which the amount of toner remaining in each subsequent sieve section is calculated by multiplying the amount by a preset coefficient.
However, these methods have a large variation in data and have a difference depending on a measurer, and it was not possible to evaluate a fine difference in fluidity between toners.
[0003]
On the other hand, carbon black is usually used as a black pigment, but this material has been pointed out as having problems in terms of safety against the human body such as carcinogenicity, and studies on alternative materials are urgently required. . Metal oxides are being studied as such candidates.
However, in the case of metal oxides, the specific gravity is large, so that a new study is required in terms of the use of fluidity when toner powder is used.
[0004]
The problem of toner fluidity has come to the fore as a problem since the low-temperature fixing of toner and oil-less fixing have begun to progress. Regarding such low-temperature fixing, there is an attempt to add a specific non-olefinic crystalline polymer having a sharp melt property at a glass transition temperature to a binder (Japanese Patent Application Laid-Open No. 62-63940). There is also an attempt to use crystalline polyester having the same sharp melt property (Japanese Patent No. 2931899, Japanese Patent Application Laid-Open No. 2001-222138).
[0005]
However, crystalline polyesters having a sharp melt property at the glass transition temperature, when the product temperature during kneading is higher than the glass transition temperature, reduce the kneading shear force, dispersibility of the wax and dispersibility of the crystalline polyester resin itself. Easy to worsen. In particular, in a full-color toner using a resin having a small elastic component, the dispersibility is significantly deteriorated. Therefore, problems such as a decrease in fluidity due to a decrease in wax dispersibility and a decrease in transparency due to a decrease in dispersibility of the crystalline polyester resin are likely to occur.
[0006]
The image quality of copiers, printers, and the like has been increasing, and recently, the reproducibility of fine dots has become very important. The reproducibility of this dot is greatly affected by the fluidity in addition to the charge amount of the toner and the developer, and it is necessary to stably supply and transport a uniform toner layer or developer layer on the fine latent image portion. Is becoming necessary.
Further, as the image quality is improved, the particle size and the function of the toner used for the toner are advanced. For this reason, the structure of the toner has become more complicated, and it is necessary to perform finer control at the time of production than before. In particular, since the fluidity of the toner affects various image qualities in addition to the dot reproducibility, a highly accurate evaluation method that does not differ between individuals in terms of evaluation is required.
[0007]
Furthermore, when the production method of the toner changes from a pulverization method to another method such as a polymerization method, a change in the flow characteristics with respect to the production conditions is large, and finer control in the production compared to the pulverization method. And evaluation is needed.
Further, with the progress of low-temperature fixing of the toner and oil-less fixing, the base composition and structure of the toner become complicated, and the fluidity of the toner is affected. Therefore, structural control with higher precision than before is required, and accordingly, a fluidity evaluation method with high sensitivity is required.
[0008]
[Patent Document 1]
JP-A-01-203941
[Patent Document 2]
JP 04-116449 A
[Patent Document 3]
JP 2000-292967 A
[0009]
[Problems to be solved by the invention]
The present invention uses a metal oxide that can obtain high image quality at any time without problems in toner transportability, high image density, and good dot reproducibility by using an evaluation method with high fluidity accuracy and no individual differences. An object of the present invention is to make it possible to stably produce a toner for developing an electrostatic image that is safe for a human body using the toner.
Further, the present invention proposes an evaluation method which is more accurate than conventional methods, is quantitative, and can be measured without individual differences, specifies the optimal fluidity conditions of the toner using metal oxide, and sets the toner in a short time. It is an object of the present invention to stably produce a toner for developing an electrostatic image capable of measuring a phase as it is, introducing it into a production line, and obtaining high image quality. Further, the present invention provides a toner for developing an electrostatic image, which has no problem in the fluidity of the toner even when such low-temperature fixing of the toner and oil-less fixing are realized, and a stable high image quality can be obtained. With the goal.
Furthermore, the present invention provides not only high safety but also a method for evaluating the above-mentioned toner which presents conditions for realizing high image quality using a new material, a developing method using the toner, and a toner filled with the toner. It is an object to provide a cartridge, a method for manufacturing the toner, and an evaluation device.
[0010]
[Means for Solving the Problems]
According to the present invention, the following (1) to (25) are provided.
(1) An additive is adhered or fixed to the surface of a base toner powder composed of a pigment and a resin using at least a metal oxide, and after the powder has been compacted in advance, the penetration speed is 5 mm while rotating a conical rotor. / Min is 0.1 to 1.9 mNm at the time of penetration into the 20 mm powder phase, or the value of the load at the time of penetration into the 20 mm powder phase is 0.01 to 1.9 mNm. 0.37N, the toner for developing an electrostatic image.
(2) The toner for developing an electrostatic charge image according to (1), wherein the metal oxide comprises an Fe oxide and a Ti oxide.
(3) The electrostatic image developing toner according to (1) or (2), wherein the porosity of the powder phase in the compacted state is 0.50 to 0.64.
(4) The electrostatic image development according to any one of (1) to (3), wherein at least one of the resins is a crystalline polyester represented by the following general formula (1). For toner.
[-O-CO-CR₁= CR₂-CO-O- (CH₂)_n−]_m  (1)
(Where R₁, R₂Represents a hydrocarbon group, and n and m represent the number of repeating units. )
(5) The electrostatic image developing toner according to any one of (1) to (4), wherein the metal oxide has an average particle diameter of 0.01 to 0.2 μm.
(6) The electrostatic image developing toner according to any one of (1) to (5), wherein the content of the metal oxide is 20 to 100 parts by weight with respect to 100 parts by weight of the resin. .
(7) Any of the above (1) to (6), wherein a charge control agent and / or a release agent is contained in the base toner powder comprising a pigment and a resin using at least a metal oxide. The toner for developing an electrostatic image according to any one of the above items.
(8) The electrostatic image development as described in (7) above, wherein a dispersant of a release agent is contained in the powder comprising the pigment, resin and release agent using at least the metal oxide. For toner.
(9) The electrostatic charge image according to (7) or (8), wherein a pulverization aid is contained in the powder composed of the pigment, resin, and release agent using at least the metal oxide. Development toner.
(10) The additive according to (1), wherein the additive adhered or fixed to the surface of the base toner powder composed of a pigment and a resin using at least a metal oxide is an inorganic fine powder having an average particle diameter of 10 to 200 nm. The toner for developing an electrostatic charge image according to any one of (1) to (9).
(11) The additive according to (1), wherein the additive attached or fixed to the surface of the base toner powder composed of a pigment and a resin using at least a metal oxide is a charge control agent having an average particle diameter of 10 to 200 nm. The toner for developing an electrostatic charge image according to any one of (1) to (9).
(12) The electrostatic image developing toner as described in any one of (1) to (11) above, which is prepared using a composition in which a resin and a pigment are kneaded in advance.
(13) The toner according to any one of (1) to (12), wherein the average circularity of the base toner powder including the pigment and the resin using at least the metal oxide is 0.90 to 0.99. 3. The toner for developing an electrostatic image according to item 1.
(14) The electrostatic image developing toner according to any one of (1) to (13), wherein the toner has a volume average particle diameter of 4 to 10 μm.
(15) A method for evaluating a toner in which an additive is attached or fixed to the surface of a base toner powder composed of a pigment and a resin using at least a metal oxide, wherein the additive is attached to the surface of the base toner powder Alternatively, the powder of the adhered toner is brought into a compacted state, and then the powder is caused to penetrate into the powder phase at a penetration speed of 0.5 to 150 mm / min while rotating the conical rotor at a rotation speed of 0.1 to 100 rpm. A method for evaluating a toner for developing an electrostatic image, comprising measuring a torque and / or a load.
(16) The method for evaluating a toner for developing an electrostatic image according to (15), wherein the cone rotor has an apex angle of 20 to 150 °.
(17) The method for evaluating an electrostatic image developing toner according to (15) or (16), wherein a groove is formed in a surface of the conical rotor.
(18) The toner evaluation method for developing an electrostatic image according to any one of (15) to (17), wherein the number of revolutions of the conical rotor is 0.1 to 10 rpm.
(19) A one-component developing method comprising performing contact or non-contact development using the electrostatic image developing toner according to any one of (1) to (14).
(20) The one-component developing method according to (19), wherein a doctor roller and / or a supply roller are used.
(21) A two-component developing method comprising developing using the electrostatic image developing toner according to any one of (1) to (14) and a carrier having a particle size of 20 to 100 μm.
(22) The developing method according to any one of (19) to (21), wherein the development is performed by applying an AC bias voltage component.
(23) A toner cartridge characterized by being filled with the toner for developing an electrostatic charge image according to any one of (1) to (14).
(24) An electrostatic charge, wherein the toner is evaluated by the evaluation method according to any one of (15) to (18), and the toner is selected so as to satisfy the condition described in (1). Method for producing toner for image development.
(25) At least a toner container for developing an electrostatic charge image, a conical rotor, an elevator for injecting the conical rotor into the container, a torque meter and / or a load cell for measuring a load, wherein (15) A toner evaluation device for developing an electrostatic charge image, wherein the toner fluidity is evaluated by using the evaluation method according to any one of (18) to (18).
[0011]
That is, the present invention relates to a method in which an additive is adhered or fixed to the surface of a base toner powder composed of at least a pigment and a resin using a metal oxide, and the fluidity of the powder is determined after the powder is previously compacted. While rotating the conical rotor into the powder phase, it was penetrated at a penetration speed of 5 mm / min, and the torque generated when the conical rotor penetrated the powder phase by 20 mm penetrated 0.1 to 1.9 mNm or 20 mm. It is found that a toner having an occasional load of 0.01 to 0.37 N is a toner for developing an electrostatic charge image having good toner transportability, high image density, and high image quality with good dot reproducibility. Thus, the present invention has been completed.
[0012]
The present invention is characterized in that the use of a metal oxide which is safe for the human body and has a high degree of coloring as a black pigment enables the human body to be safe and high image quality can be realized. It relates to a toner for use. Specifically, using metal oxides as pigments, we developed a technology to apply to toner and realized safety and high image quality.
[0013]
The toner of the present invention has a structure in which at least the surface of a base toner powder composed of a pigment and a resin using a metal oxide is covered with an additive. Since the fluidity of the toner containing the metal oxide greatly changes depending on the compaction state, the fluidity is evaluated by changing the compaction state, and the optimal toner structure condition is selected.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described more specifically.
The following are used as the pigment used in the present invention.
Examples of the black pigment used in the present invention include a metal oxide composed of Fe oxide, Fe oxide and Ti oxide, a metal oxide composed of Gd oxide and Fe oxide, and a metal oxide composed of Mn oxide and Fe oxide. At least one kind of metal oxide, such as a product, and a mixture thereof are used. These metal oxides have a spinel structure and basically have the following composition, for example.
(AO) · Fe₂O₃
(A: Ti, Gd, Mn, Fe)
[0015]
However, in reality, the reaction is often insufficient, and Ti oxides, Gd oxides, Mn oxides, Fe oxides, and the like are often present at the grain boundaries in a segregated form. Are included as the present material.
[0016]
For example, in the case of a metal oxide composed of Fe oxide, Fe oxide and Ti oxide, it has the following composition, and is composed of FeO or TiO.₂Is increased by increasing the amount of non-magnetic pigment and can be used as a black pigment.

[0017]
In the above formula, it is preferable that the condition of 1 ≦ X <2 is satisfied. A manufacturing method when A is Ti is described below.
Ti oxide and Fe oxide are weighed and mixed using a ball mill. Next, it was calcined at 600 to 1000 ° C. for 2 to 5 hours using an electric furnace or the like, and the calcined product was put into a ball mill and pulverized. The obtained powder is pressure-formed by a powder press into a plate shape, and the formed product is fired in an electric furnace or the like at 1100 to 1300 ° C for 2 to 5 hours. The calcined product is cut with a cutter, ground and finely ground, and classified to a predetermined particle size by a classifier to obtain metal oxide particles composed of Ti oxide and Fe oxide.
The average particle size of the metal oxide particles composed of Ti oxide and Fe oxide is preferably 0.01 to 0.2 μm. If the average particle size of the metal oxide particles composed of Ti oxide and Fe oxide is smaller than 0.01 μm, aggregation or the like is likely to occur, and if the average particle size is larger than 0.2 μm, the coloring power is reduced. Not suitable.
[0018]
In the case of a metal oxide composed of an Fe oxide and a Gd oxide, it has the following composition.
Gd_xFe_3-xO₄
(In the formula, it is preferable that 0.25 ≦ x ≦ 2.)
When the Gd composition is less than 0.5, the particles have strong magnetic properties, and the particles tend to aggregate, which is not suitable for high image quality. When the Gd composition is larger than 2, the spinel structure is broken, and a stable material cannot be obtained.
[0019]
Since the magnetic properties of the metal oxide change in accordance with the Gd composition, it is possible to produce both a one-component magnetic toner and a two-component non-magnetic toner. As the Gd composition increases, the magnetic properties decrease and change from ferromagnetic to non-magnetic (the changes in magnetic properties with respect to the Gd composition are shown in the examples). When used as a magnetic toner, the Gd composition x needs to be 0.25 ≦ x <0.5. When used as a non-magnetic toner, it is necessary that 0.5 ≦ x ≦ 2.
[0020]
As a method for manufacturing a metal oxide composed of a Gd oxide and an Fe oxide, the following methods are available.
Gd oxide and Fe oxide are weighed and mixed using a ball mill. Next, it was calcined at 600 to 1000 ° C. for 2 to 5 hours using an electric furnace or the like, and the calcined product was put into a ball mill and pulverized. The obtained powder is pressure-formed by a powder press into a plate shape, and the formed product is fired in an electric furnace or the like at 1100 to 1300 ° C for 2 to 5 hours. This calcined product is cut with a cutter, ground and finely ground, and classified into a predetermined particle size by a classifier to obtain metal oxide particles composed of Gd oxide and Fe oxide.
[0021]
The average particle size of the metal oxide particles composed of Gd oxide and Fe oxide is preferably 0.01 to 0.2 μm. If the average particle size of the metal oxide particles composed of Gd oxide and Fe oxide is smaller than 0.01 μm, aggregation or the like is likely to occur, and if the average particle size is larger than 0.2 μm, the coloring power is reduced. Not suitable.
[0022]
Gd oxide is a stable material, has been found to be safe for the human body, and has been used for medical purposes. Therefore, a metal oxide composed of a Gd oxide and an Fe oxide is a material that is completely safe for the human body.
[0023]
Further, a third additive may be added to these materials.
For example, in the present invention, there is provided a toner for developing an electrostatic image, wherein the additive B in the following formula is Mg, Al, Si, Ti, Cr, Mn, Co, Ni, Cu, Zn or Ga. .
Gd_x(Fe_1-yB_y)_3-xO₄
(In the formula, 0.25 ≦ x ≦ 2, 0 ≦ y ≦ 0.5.)
[0024]
The third additive B is added when the magnetic properties are too strong, or when the durability is reinforced. The amount of the additive corresponds to the amount of y in the above formula. When the amount of addition is large, a separated phase is formed, and it is difficult to produce a structurally stable material. Therefore, the addition amount y is preferably set to 0.5 or less.
[0025]
Further, in the present invention, it is also possible to mix a metal oxide with a conventionally used black pigment. Examples of black pigments include azine dyes such as carbon black, oil furnace black, channel black, lamp black, acetylene black, and aniline black, metal salt azo dyes, metal oxides, and metal composite oxides.
[0026]
When a toner is prepared using the present metal oxide, the content of the metal oxide composed of Ti oxide, Fe oxide, and the like is preferably 20 to 100 parts by weight based on 100 parts by weight of the resin. If the amount is less than 20 parts by weight, the image density decreases and the sharpness of the image also decreases. Conversely, when the amount is more than 100 parts by weight, the fixing characteristics are deteriorated, and the durability characteristics such as toner scattering are deteriorated.
[0027]
When the metal oxide is used as a pigment in this way, the specific gravity of the material itself is different and the content thereof is also different, so that the fluidity of the toner particles needs to be newly optimized. The toner fluidity required for image quality improvement was specified.
[0028]
As the resin, a crystalline polyester may be used. Aliphatic polyesters having crystallinity, a sharp molecular weight distribution, and having the absolute amount of the low molecular weight as much as possible are preferred. This resin undergoes crystal transition at the glass transition temperature (Tg), and at the same time, its melt viscosity sharply decreases from the solid state, and exhibits a fixing function to paper. By using this crystalline polyester resin, low-temperature fixing can be achieved without excessively lowering the Tg or molecular weight of the resin. Therefore, there is no decrease in preservability due to a decrease in Tg. Also, there is no deterioration in gloss and offset resistance that are too high due to the reduction in molecular weight. Therefore, the introduction of the crystalline polyester resin is very effective in improving the low-temperature fixability of the toner.
[0029]
In the present invention, the aliphatic crystalline polyester is preferably represented by the following general formula (1).
[-O-CO-CR₁= CR₂-CO-O- (CH₂)_n−]_m  (1)
(Where R₁, R₂Represents a hydrocarbon group, and n and m represent the number of repeating units. )
[0030]
In the toner of the present invention, in order to exhibit low-temperature fixability and ensure hot offset resistance, the content of the crystalline polyester is 1 to 50 with respect to the total amount of the resin and the release agent in the toner. % By weight, and the content of the release agent is preferably 2 to 15% by weight. When the content of the crystalline polyester is less than 1% by weight, there is no effect on the low-temperature fixability, and when it exceeds 50% by weight, the hot offset property deteriorates. When the content of the release agent is less than 2% by weight, there may be no effect on the anti-offset property, and when it exceeds 15% by weight, the fluidity of the toner decreases.
[0031]
Other resins include polyester resins and / or polyol resins conventionally used for color toners. Polyester resins and polyol resins are suitable because they have better low-temperature fixability and relatively good heat-resistant storage properties than styrene-acrylic resins that have been frequently used in the past. However, polyester resins and polyol resins have poor dispersibility of the release agent as compared with styrene-acrylic resins. If the dispersibility is poor, the pulverizing stress tends to concentrate on the interface between the resin and the wax at the time of pulverization, so that it is easy to be pulverized at the interface between the resin and the release agent, and the ratio of the added release agent to the surface of the pulverized toner The release agent was exposed to the toner, and the fluidity of the toner was deteriorated.
Therefore, the toner of the present invention can realize high image quality by defining the toner flow to be in an optimum condition without any problem.
[0032]
The evaluation method of the toner for developing an electrostatic image according to the present invention is such that the conical rotor is caused to enter (down) or to be pulled out (up) while rotating the conical rotor in the powder phase. Is to measure the torque and load applied to the container containing the, and to evaluate the fluidity based on the value of the torque and load. The shape of the conical rotor may be of any shape, but a cone having an apex angle of 20 to 150 ° is suitable. If the apex angle of the cone is less than 20 °, the resistance to the toner powder phase is small, so the torque and load are small, and a fine difference in fluidity cannot be evaluated. Conversely, if the apex angle is larger than 150 °, the force in the direction of pressing down the toner powder phase becomes large, and the toner particles are likely to be deformed, which is not suitable for evaluation of toner fluidity. The length of the conical rotor needs to be long enough so that the conical rotor surface is continuously present in the toner powder phase.
[0033]
Further, it is preferable that a groove is formed on the surface of the conical rotor. Instead of measuring the friction component between the material surface of the conical rotor and the toner particles, it is better to measure the friction component between the toner particles. To this end, when the conical rotor rotates and penetrates into the toner powder phase, the toner particles enter into the grooves cut on the surface of the conical rotor, and the entered toner particles and the surrounding toner It is more suitable to measure the state of friction with the particles. The shape of the groove is not limited, but it is necessary to devise such a way that the contact between the material surface of the conical rotor and the toner particles is reduced. An example is shown in FIG. In this method, a groove is cut straight from the vertex of the cone to the bottom side, and the cross section of the groove has a saw-tooth shape composed of triangular irregularities. In this case, the contact between the material surface of the conical rotor and the toner particles is only at the tip of the peak of the triangular groove. Mostly, the toner particles that have entered the grooves come into contact with the toner particles around the toner particles. Any material may be used for the conical rotor, but a material that is easy to process, has a hard surface, and does not deteriorate is preferable. In addition, a material that does not take chargeability is suitable. Examples of this include SUS (stainless steel), Al, Cu, Au, Ag, and brass.
[0034]
The torque and the load of the toner powder change depending on the rotation speed of the conical rotor and the penetration speed of the conical rotor. In the evaluation method of the present invention, in order to improve the accuracy of the measurement, the rotation speed and the penetration speed of the conical rotor are reduced so that the fine contact state between the toner particles can be measured. Therefore, the measurement conditions are as follows.
・ Number of rotations of conical rotor: 0.1 to 100 rpm
-Penetration speed of conical rotor: 0.5 to 150 mm / min
[0035]
If the rotation speed of the conical rotor is smaller than 0.1 rpm, the toner is likely to be affected by the delicate state of the toner powder phase. If the rotation speed is more than 100 rpm, scattering of the toner occurs and the measurement cannot be performed stably, which is not suitable. When the penetration speed of the conical rotor is lower than 0.5 mm / min, it is not suitable for the measurement because it is easily affected by the delicate state of the toner powder phase and a measurement variation problem occurs. If the speed is higher than 150 mm / min, the toner powder phase is likely to be in a compacted state, and the influence of toner deformation or the like appears, which is not suitable for fluidity evaluation.
[0036]
The configuration of the evaluation device of the present invention is, for example, as shown in FIG. 1, in which a conical rotor is attached to the tip of a shaft and fixed to a torque meter. The torque meter can be moved up and down by an elevator, so that a container containing toner is placed at the center of the stage, and by lowering the conical rotor, the conical rotor rotates and enters the center of the container while rotating. I do. The torque applied to the conical rotor is detected by a torque meter provided above, and the load applied to the container containing the toner is detected by a load cell provided below the container. The amount of movement of the conical rotor is determined by a position detector. This configuration is an example, and other configurations such as raising and lowering the container containing the toner by an elevator may be used.
[0037]
As described above, the shape of the conical rotor preferably has an apex angle of 20 to 150 ° (see FIG. 2). The length of the conical rotor must be long enough so that the conical rotor portion can enter the interior of the toner phase sufficiently. The shape of the groove may be any shape, but care must be taken so that torque and load values are not reproduced due to replacement of the conical rotor. For this purpose, the groove shape of the conical rotor is simple, and it is better that the rotor having the same shape can be made many times (see FIG. 3). The material of the container is not limited, but a conductive material is suitable so as not to be affected by charging with the powder. In addition, since the measurement is performed while replacing the powder, it is preferable that the surface is close to a mirror surface to reduce dirt. The size of the container is important, and it is necessary to select a larger size (diameter) relative to the diameter of the conical rotor so that the wall of the container does not affect when the conical rotor enters while rotating.
[0038]
A high-sensitivity type torque meter is preferable, and a non-contact type torque meter is suitable. Load cells with a wide load range and high resolution are suitable. The position detector includes a linear scale, a displacement sensor using light, and the like, and a specification of 0.1 mm or less is suitable for accuracy. It is preferable that the elevator can be driven with high accuracy using a servomotor or a stepping motor.
[0039]
For the measurement, a certain amount of toner is put into a container, and the container is set. Thereafter, the conical rotor is caused to enter the toner powder phase while rotating. However, in the actual measurement, the toner powder phase is pressurized before the conical rotor enters, to create a compact state, and the conical rotor is lowered to the compacted toner phase for measurement. When the torque or load measurement is started, the measurement is performed at the determined number of revolutions and penetration speed. The direction of rotation of the conical rotor is arbitrary. When the penetration distance of the conical rotor is shallow, the values of torque and load are small, which causes a problem in data reproducibility and the like. Therefore, it is better to make the conical rotor penetrate deeply into a region where data can be reproduced. According to our experimental results, almost stable measurement was possible if the penetration was 5 mm or more.
[0040]
The measurement mode can be set under any conditions. For example, the following measurement modes are available.
(1) Fill the container with the toner.
(2) The toner powder phase is pressurized to create a compact state.
{Circle around (3)} The conical rotor is caused to enter while rotating, and the torque and load at that time are measured.
{Circle around (4)} When the conical rotor has penetrated from the toner surface layer to a predetermined depth, the penetrating operation is stopped.
(5) The operation of pulling out the conical rotor is started.
{Circle around (6)} When the tip of the conical rotor comes out of the surface of the toner powder phase and becomes completely free (first home position), the operation of pulling out the conical rotor is stopped and the rotation is stopped.
The above operations (1) to (6) are repeated to measure. It may be performed continuously.
[0041]
As another measurement method, the toner powder phase is stabilized by applying a vibration by a vibrator before measurement, and the stabilized toner powder phase is pressurized to a compacted state. The conical rotor is made to penetrate while rotating in the phase, the torque and load at that time are measured, and when the conical rotor reaches a preset depth, the penetrating operation is stopped, and then the conical rotor is raised to the initial position (home position).
Still another measurement method includes a method in which a conical rotor is made to penetrate into a toner powder phase in a compacted state, and a depth until a predetermined torque value is obtained.
[0042]
In the measurement method of the present invention, the porosity of the toner powder phase is important, but our experiments showed that the measurement was stable when the porosity was 0.5 or more. If it is less than 0.5, it takes a long time to produce a compacted state, and continuous measurement is difficult. The range of the porosity of the toner powder phase was 0.5 to 0.64 including various measurement methods. If it is larger than 0.64, it is not possible to cope with the actual use conditions of the apparatus or the like, and it is not suitable for measurement. This change in the porosity is created by applying a load or the like to the toner powder phase.
[0043]
In the present invention, the compacted state is not a released state but a state in which powder is filled in a closed state such as a container and rearranged by various methods.
The porosity of the toner powder phase indicates the ratio of the gap existing in the powder phase, and is determined by the following equation.
Porosity = (bulk volume-true volume) / true volume
However, the measurement system, measurement conditions, and the like are not limited to this.
[0044]
The toner of the present invention preferably has a volume average particle diameter of 4 to 10 μm in order to realize a high quality image. More preferably, it is 4 to 7 μm. If the volume average particle diameter is less than 4 μm, problems such as contamination inside the apparatus due to toner scattering during long-term use, a decrease in image density in a low-humidity environment, poor photoconductor cleaning, and the like are likely to occur, and there is a concern about the effect on the human body. When the volume average particle size exceeds 10 μm, the resolution of the minute spots of 100 μm or less is not sufficient, and the fine spots tend to be scattered to non-image portions, resulting in poor image quality.
[0045]
In the developer using the toner of the present invention, the carrier preferably has an average particle diameter of 20 to 100 μm in order to realize a high quality image. When the average particle size of the carrier is in the range of 20 to 100 μm, the charge amount of the toner can be made more uniform when the toner concentration in the developing device is in the range of 2 to 10% by weight. If it is less than 20 μm, the carrier particles are likely to adhere to the photoreceptor, and the stirring efficiency with the toner is deteriorated, so that it is difficult to obtain a uniform charge amount of the toner. Conversely, when the average particle size of the carrier exceeds 100 μm, fine image reproducibility deteriorates, and high image quality cannot be obtained.
Details of the toner and the developer are shown below.
[0046]
The resin preferably contains an aliphatic crystalline polyester, and the molecular structure of the crystalline polyester resin is not limited. From the viewpoint of the crystallinity and softening point of the polyester resin, the resin has 2 to 6 carbon atoms. Diol compounds, in particular, an alcohol component containing 1,4-butanediol, 1,6-hexanediol and derivatives thereof, and an acid component containing maleic acid, fumaric acid, succinic acid, and derivatives thereof. It is preferable to contain an aliphatic polyester represented by the following general formula (1), which is synthesized by:
[-O-CO-CR₁= CR₂-CO-O- (CH₂)_n−]_m  (1)
(Where R₁, R₂Is a hydrocarbon group, and n and m are the number of repeating units. )
Also, from the viewpoint of the crystallinity and softening point of the polyester resin, a trihydric or higher polyhydric alcohol such as glycerin is added to the alcohol component to synthesize a non-linear polyester, and trimellitic anhydride or the like is added to the acid component. Condensation polymerization may be carried out by adding a trivalent or higher polycarboxylic acid.
[0047]
The glass transition temperature (Tg) of the crystalline polyester resin is desirably low as long as the heat-resistant storage stability is not deteriorated, and is preferably in the range of 80 to 130 ° C.
When the glass transition temperature (Tg) is 80 ° C. or lower, the heat-resistant storage stability deteriorates, and blocking tends to occur at the temperature inside the developing device. No longer available. The glass transition temperature (Tg) of the crystalline polyester resin is an endothermic peak temperature at the time of a 2nd temperature rise by DSC.
[0048]
As the resin, other than the aliphatic crystalline polyester represented by the general formula (1), all resins conventionally used as toner resins can be used, such as polystyrene resin and epoxy resin. , Polyester resin, polyamide resin, styrene-acryl resin, styrene-methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene-butadiene resin, phenol resin, polyethylene resin, silicone resin, butyral resin, terpene resin, polyol resin, etc. .
[0049]
Examples of the vinyl resin include styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene, and homopolymers of substituted styrenes: styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, and styrene-vinyltoluene copolymer. Polymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacryl Methyl acrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Coalescence, styrene-vinyl ethyl acetate Copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene-based copolymers such as copolymers: polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate and the like.
[0050]
The polyester resin is composed of a dihydric alcohol component as shown in Group A below, a dibasic acid component as shown in Group B, and a trivalent or higher alcohol as shown in Group C. Alternatively, a carboxylic acid may be added as a third component.
[0051]
Group A: ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,4-bis (hydroxymethyl ) Cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylene (2,2) -2,2'-bis (4-hydroxyphenyl) propane, polyoxypropylene (3,3)- 2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2,0) -2,2′-bis (4-hydroxyphenyl) propane and the like.
[0052]
Group B: maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid, linoleic acid, or Esters of these acid anhydrides or lower alcohols.
[0053]
Group C: trihydric or higher alcohol such as glycerin, trimethylolpropane, pentaerythritol and the like, and trivalent or higher carboxylic acid such as trimellitic acid and pyromellitic acid.
[0054]
As the polyol resin, an epoxy resin and an alkylene oxide adduct of a dihydric phenol, or a compound having one active hydrogen in the molecule that reacts with the glycidyl ether and the epoxy group, and an active hydrogen that reacts with the epoxy resin in the molecule. There are compounds obtained by reacting two or more compounds.
[0055]
The metal oxide described above is used as the pigment used in the present invention.
In toners, good pigment uniform dispersion is essential.Instead of directly charging the pigment into a large amount of resin, a masterbatch in which the pigment is once dispersed at a high concentration is prepared and injected in a form that dilutes it. Is used. In this case, a solvent is generally used to help dispersibility, but there are environmental problems and the like, and in the present invention, water is used to disperse. When water is used, temperature control is important so that residual moisture in the masterbatch does not matter.
[0056]
It is preferable that a charge control agent is blended (internally added) into the toner particles of the present invention. However, they may be mixed (externally added) with the toner particles. The charge control agent makes it possible to control the charge amount optimally according to the development system. In particular, in the present invention, the balance between the particle size distribution and the charge amount can be further stabilized.
[0057]
Nigrosine and quaternary ammonium salts, triphenylmethane dyes, imidazole metal complexes and salts can be used alone or in combination of two or more to control the toner to have a positive charge. Further, a metal salicylate complex, salts, organic boron salts, calixarene-based compounds, and the like are used to control the toner to have a negative charge.
[0058]
Further, a release agent can be internally added to the toner of the present invention in order to prevent offset during fixing. Release agents include natural waxes such as candelilla wax, carnauba wax, and rice wax, montan wax and its derivatives, paraffin wax and its derivatives, polyolefin wax and its derivatives, sasol wax, low molecular weight polyethylene, and low molecular weight polypropylene. And alkyl phosphate esters. The melting point of these release agents is preferably from 65 to 90 ° C. If the temperature is lower than this range, blocking during storage of the toner tends to occur. If the temperature is higher than this range, offset may easily occur in a region where the temperature of the fixing roller is low.
[0059]
An additive may be added for the purpose of improving the dispersibility of the release agent and the like. As additives, styrene-acrylic resin, polyethylene resin, polystyrene resin, epoxy resin, polyester resin, polyamide resin, styrene-methacrylate resin, polyurethane resin, vinyl resin, polyolefin resin, styrene-butadiene resin, phenolic resin, butyral resin, There are terpene resins, polyol resins, and the like, and a mixture of two or more of each resin may be used.
[0060]
Further, a pulverization aid may be included in the present toner in order to improve the pulverizability. Examples of the material include a resin containing a polymer of at least one monomer selected from the group consisting of vinyl toluene, α-methylstyrene, and isopropenyl toluene. The present polymer may be a homopolymer of vinyl toluene, α-methylstyrene or isopropenyl toluene, or a copolymer of these monomers. It is preferable that other monomers other than styrene are not copolymerized in these polymers, but other monomers other than styrene may be copolymerized as long as the object of the present invention is not impaired.
[0061]
The styrene content is desirably 50 mol% or less, preferably 20 to 40 mol%, as the proportion of styrene in all the monomers constituting the copolymer. Since these resins are brittle, when used in combination with crystalline polyester, insufficient pulverizability due to the crystallinity of the crystalline polyester can be improved.
[0062]
When a magnetic toner is used, fine particles of a magnetic substance may be internally added to the toner particles. As the magnetic material, a ferromagnetic material such as ferrite, magnetite, iron, nickel, cobalt, or an alloy thereof can be considered. The average particle size of the magnetic material is preferably 0.1 to 1 μm. The content of the magnetic material is preferably 10 to 70 parts by weight based on 100 parts by weight of the toner.
[0063]
Further, as described above, the toner of the present invention adheres or fixes inorganic fine powder on the toner surface as a fluidity improver. The average particle size of the inorganic fine powder is suitably from 10 to 200 nm. If the particle size is smaller than 10 nm, it is difficult to create an uneven surface having an effect on fluidity. If the particle size is larger than 200 nm, the shape of the powder becomes rough and the problem of the toner shape occurs.
[0064]
Examples of the inorganic fine powder of the present invention include Si, Ti, Al, Mg, Ca, Sr, Ba, In, Ga, Ni, Mn, W, Fe, Co, Zn, Cr, Mo, Cu, Ag, V, and Zr. Oxides and composite oxides. Among them, fine particles of silicon dioxide (silica), titanium dioxide (titania), and alumina are preferably used.
[0065]
Further, it is effective to perform a surface modification treatment with a hydrophobizing agent or the like. The following are typical examples of the hydrophobizing agent.
Dimethyldichlorosilane, trimethylchlorosilane, methyltrichlorosilane, allyldimethyldichlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, p-chloroethyltrichlorosilane, Chloromethyldimethylchlorosilane, chloromethyltrichlorosilane, hexaphenyldisilazane, hexatolyldisilazane and the like.
[0066]
The inorganic fine powder is preferably used in an amount of 0.1 to 2% by weight based on the toner. If it is less than 0.1% by weight, the effect of improving toner aggregation is poor. If it exceeds 2% by weight, problems such as toner scattering between fine lines, contamination inside the machine, scratches and abrasion of the photoreceptor tend to occur. is there.
[0067]
Further, a charge control agent may be attached or fixed to the surface of a powder composed of at least a resin and a pigment so that the powder surface has a small cycle and a large cycle. The average particle size is optimally as small as 10 to 200 nm. If the particle size is smaller than 10 nm, it is difficult to create an uneven surface having an effect on fluidity. If the particle size is larger than 200 nm, the shape of the powder becomes rough and the problem of the toner shape occurs. Examples of charge control agents include nigrosine and quaternary ammonium salts, triphenylmethane dyes, imidazole metal complexes and salts, salicylic acid metal complexes and salts, organic boron salts, calixarene compounds, and the like. Is also good.
[0068]
The toner of the present invention may further contain other additives within a range that does not substantially adversely affect the toner, for example, lubricant powders such as Teflon (R) powder, zinc stearate powder, polyvinylidene fluoride powder; or cerium oxide powder. Polishing agents such as silicon carbide powder and strontium titanate powder; or a small amount of a conductivity-imparting agent such as carbon black powder, zinc oxide powder, tin oxide powder and the like can be used as a developability improver.
[0069]
Examples of a method for producing the toner according to the present invention include a pulverization method and a polymerization method (suspension polymerization, emulsion polymerization / dispersion polymerization, emulsion aggregation, emulsion association, and the like), but are not limited thereto.
[0070]
As an example of the pulverization method, first, the above-described resin, a pigment or dye as a colorant, a charge control agent, a release agent, other additives, and the like are sufficiently mixed by a mixer such as a Henschel mixer, and then a batch type is used. The components are well kneaded using a hot kneader such as a two-roll mill, a Banbury mixer, a continuous twin screw extruder, or a continuous single screw kneader, and after rolling and cooling, cutting is performed. The kneaded toner after cutting is crushed, coarsely crushed using a hammer mill or the like, further finely crushed using a fine crusher or a mechanical crusher using a jet stream, and a classifier using a swirling air stream or a Coanda effect. The particles are classified to a predetermined particle size by a classifier using. Thereafter, an additive composed of inorganic particles or the like is attached or fixed to the particle surface by a mixer. The fluidity of the toner particles after the mixing step is evaluated using the present evaluation method. In this case, in the sampling inspection, a sample is put into a sample container, and the sample is brought into a compacted state by pressurizing or the like, and the sample container is directly placed on a sample table of the evaluation apparatus shown in FIG. 1 for measurement. The rotation speed of the conical rotor was 0.1 to 10 rpm, and the penetration speed of the conical rotor was 5 mm / min. In the measurement, the conical rotor is rotated to penetrate, and after a predetermined penetration distance of 5 mm or more, the penetration is stopped, and then the conical rotor is pulled out and returned to the original initial position. The torque and the load when the conical rotor enters the toner powder phase are measured to evaluate the fluidity of the toner.
[0071]
When the toner fluidity is evaluated by the evaluation method of the present invention, the measured value (torque, load) and the toner fluidity have the following relationship.
When the torque is small, the fluidity is good.
If the torque is large, the fluidity is poor.
When the load is small, the fluidity is good.
When the load is large, the fluidity is poor.
[0072]
The features of the evaluation method of the present invention using a conical rotor are as follows, and a sample can be measured quickly and easily as it is, so that highly accurate measurement without individual differences can be performed.
(1) Non-destructive inspection.
(2) The sample can be measured as it is.
(3) Measurement can be performed in a short time.
(4) Anyone can easily measure.
Therefore, measurement on a production line is also possible, and it can be installed between each process in a production process, and quality evaluation can be performed in the middle of the process. For example, after the mixing step, a sample extraction / measurement zone is provided in the course of transporting the powder sample to the next step, and a shutter is opened and closed at a certain timing to transport a fixed amount of the sample to the measurement unit. The tip of the measuring part is a container made of SUS or the like, and the measurement is directly performed by the present evaluation method. Alternatively, the container is brought to the present evaluation device in another nearby place, placed on a sample stage, and measured by the present evaluation method. As a result of the evaluation, if the numerical value is out of the predetermined setting range, the sample is not sent to the filling process but is sent to the toner reprocessing process. These mechanisms can be applied to inspection after the pulverizing / classifying step, which is a step before the mixing step, inspection after the air sieving step after the mixing step, inspection before filling, and the like (see FIG. 4).
Further, the toner evaluation device having these functions can be used alone as an evaluation device in the development stage.
[0073]
In the case of toner, the measured values of torque and load in this evaluation method indicate fluidity as described above, and quantitative evaluation is possible. In the conventional evaluation method up to now, the difference between toners can be evaluated, but there is a problem that if the type of toner is different, it cannot be evaluated in the same playing field. However, the values measured by this evaluation method are torque values and load values as powder characteristics, and values that can be evaluated on the same ring even if the type of toner changes or the particle size changes. Evaluation value.
[0074]
The torque and load characteristics of the conical rotor during the movement of the conical rotor in the toner powder phase are closely related to the fluidity of the powder. It is easy to move because of its small adhesive force, and even if the conical rotor is moved in the powder phase, the torque is small and the load change is small. On the other hand, when the fluidity of the powder is poor, it is difficult to move due to the large adhesive force between the individual powder particles. And the force (load) acting in the downward direction also increases. In particular, this phenomenon appears as a subtle change when a release agent or the like is put into the toner, and the adhesive force between the individual powder particles appears more remarkably in a compacted state. Therefore, it is necessary to evaluate the fluidity of the toner in the compacted state.
[0075]
Therefore, according to the evaluation method of the present invention, the fluidity can be evaluated based on the following relationship.
When fluidity is good → The torque and load when moving in the compacted powder phase are small.
When the fluidity is poor → The torque and load when moving in the powder phase in the compacted state are large.
[0076]
The fluidity of the toner is largely determined by the mixing process in the toner production process. That is, the fluidity of the toner particles greatly changes depending on the state in which the additive composed of the inorganic particles or the like is attached or fixed to the surface of the toner particles.
The mixing state of the toner varies depending on the mixing conditions (feed amount, rotation speed, mixing time, etc.) in the mixing step. Therefore, the mixing conditions play an important role in the fluidity, and the evaluation of the fluidity after the mixing step is important.
[0077]
In a printer or a copying machine, in order to realize high image quality, it is necessary to enhance the reproducibility of very minute dots. To achieve this, toner development that is faithful to very small latent images is required. In order to enable this faithful development, it is necessary to transport and supply a uniform toner brush to the development area. For this purpose, it is necessary that the toner charge amount is in an appropriate condition, but the ease of movement of the toner and the ease of transport so that a stable and uniform toner brush can be supplied to the development area are extremely high. It becomes important. That is, in order to increase the reproducibility of minute dots, it is necessary to increase the fluidity of the toner. In particular, in the case of a toner containing a release agent, it is necessary to increase the fluidity in a compacted state.
[0078]
Therefore, the fluidity of the toner of the present invention using a metal oxide as a pigment was evaluated by the evaluation method of the present invention using a conical rotor, and the relationship between dot reproducibility and toner transportability was examined. There is a correlation, and when the torque and the load are small, the dot reproducibility and the toner transportability are improved.
From the results, it was found that the toner using the metal oxide capable of improving the image quality exhibited the following torque and load characteristics.
[0079]
{Circle around (1)} The value of the torque when the conical rotor enters (when the conical rotor enters 20 mm) is 0.1 to 1.9 mNm.
{Circle around (2)} The value of the load when the conical rotor enters (when the conical rotor enters 20 mm) is 0.01 to 0.37N.
(Here, the penetration speed of the conical rotor: 5 mm / min, the space ratio: 0.50 to 0.64)
Note that other methods can be used for the evaluation mode without any problem. The evaluation item may be an intrusion distance to a certain load, an intrusion distance to a certain torque, or the like other than the torque and the load, or an integrated value of the torque and the load. Further, other evaluation items may be used.
[0080]
The toner of the present invention is obtained by passing through a sieve of 250 mesh or more after the mixing step to remove coarse particles and aggregated particles.
[0081]
As a method for producing the toner according to the present invention, a method other than the pulverization method is considered. As an example of the polymerization method, a monomer composition obtained by adding a colorant (pigment) and a charge control agent to a monomer is used in an aqueous medium. The toner particles are obtained by suspending and polymerizing in the suspension. The granulation method is not particularly limited.
[0082]
For example, the toner of the present invention is obtained by dissolving at least an isocyanate group-containing polyester prepolymer in an organic solvent, dispersing a pigment colorant, and dissolving or dispersing a release agent in an aqueous medium. Urea-modified polyester resin having a urea group by dispersing the prepolymer in the dispersion in the presence of inorganic fine particles and / or polymer fine particles and reacting the prepolymer with a polyamine and / or a monoamine having an active hydrogen-containing group in the dispersion. Is formed, and the liquid medium contained therein is removed from the dispersion containing the urea-modified polyester resin.
The urea-modified polyester resin has a Tg of 40 to 65 ° C, preferably 45 to 60 ° C. Its number average molecular weight Mn is 2,500 to 50,000, preferably 2,500 to 30,000. Its weight average molecular weight Mw is 10,000 to 500,000, preferably 30,000 to 100,000.
[0083]
This toner contains, as a binder resin, a urea-modified polyester-based resin having a urea bond and having a high molecular weight by a reaction between the prepolymer and the amine. The coloring agent is highly dispersed in the binder resin.
The obtained dried toner powder is subjected to air classification, and an additive composed of inorganic fine particles or the like is attached or fixed to the particle surface by a mixer under the above-described optimum mixing conditions. Alternatively, the charge control agent may be injected into the dried toner powder surface and fixedly injected. After that, an additive such as inorganic fine particles may be attached or fixed to the particle surface. By driving the charge control agent onto the surface, the charge amount of the toner can be easily controlled.
[0084]
In each production method, as a specific means of mixing or fixed injection, a method of applying an impact force to the powder mixture by a high-speed rotating blade, throwing the powder mixture into a high-speed air stream, accelerating, There is a method of colliding particles or composite particles with an appropriate collision plate. As the equipment, Angular mill (manufactured by Hosokawa Micron), I-type mill (manufactured by Nippon Pneumatic) was modified to reduce the pulverized air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), Kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar and the like.
[0085]
In the case of these methods also, inspection after granulation, inspection after treatment of charge control agent, inspection after mixing process of additives, inspection after air sieving process after mixing process, inspection before filling etc. Applicable.
Further, the evaluation method of the present invention can be used for a toner produced by a polymerization method, a spray drying method, or the like, which is produced without using a kneading step or a pulverizing step, and a capsule toner.
[0086]
Further, the fluidity of the toner is affected by the shape of the toner particles. In the case of a very spherical toner having an average circularity of 0.90 to 0.99, excellent fluidity and excellent dot reproducibility are obtained. Excellent high image quality can be realized.
[0087]
Further, the circularity of the toner particles is calculated as an average circularity by a flow type particle image analyzer FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.).
[0088]
The toner of the present invention is used as a one-component developer used in a contact or non-contact developing system. Various known contact or non-contact development systems are used. For example, there are a contact developing method using an aluminum sleeve, a contact developing method using a conductive rubber belt, and a non-contact developing method using a developing sleeve in which a conductive resin layer containing carbon black or the like is formed on the surface of an aluminum tube. . When an AC bias voltage component is applied during development using the toner of the present invention, development efficiency is improved, and image characteristics are improved.
[0089]
Further, in the one-component developing method, the present toner is used in a developing method in which a roller-shaped blade for uniforming a toner layer is provided at an outlet of a toner supply unit. In such a system, not only filming on the photosensitive member but also filming on the doctor roller occurs. For this reason, not only can the toner layer not be formed uniformly, but also the toner charging becomes non-uniform, and the toner charge becomes small. For this reason, defective development occurs.
However, when the toner of the present invention is used, filming to the doctor roller does not occur, stable development is performed, and a system having excellent durability characteristics is obtained (see FIG. 5).
[0090]
Since the toner of the present invention has excellent fluidity, it can be sufficiently stored in a cartridge container, and is also suitable for an apparatus configured to transport toner from the cartridge container to the developing unit.
[0091]
Further, when used as a two-component developer, a two-component developer is obtained by mixing with a magnetic carrier at a predetermined mixing ratio.
[0092]
As the carrier used for the two-component developer, known carriers can be used. For example, magnetic particles such as iron powder, ferrite powder, nickel powder, and magnetite powder, or the surface of these magnetic particles is coated with a fluororesin or vinyl resin. And those treated with a silicone resin or the like, or magnetic particle-dispersed resin particles in which magnetic particles are dispersed in a resin. The average particle size of these magnetic carriers is preferably 20 to 100 μm. Preferably, it is 20 to 70 μm.
[0093]
【Example】
Hereinafter, Examples will be described, but they do not limit the present invention in any way.
[0094]
(Evaluation)
In the evaluation of the toner, a toner in which the toner composition, the toner preparation method, and the mixing conditions were changed was prepared, the toner fluidity was evaluated using the evaluation method of the present invention, and the image density and dot reproducibility were evaluated as a roughness of the image. It was graded (rank 1: bad → rank 5: good).
In addition, a running durability test was performed on 20,000 sheets, and defects in toner transportability such as blocking in the developing section were evaluated. The case where there was no defect was evaluated as ○, and the case where there was a defect was evaluated as x.
The fluidity of the toner was measured by measuring the torque and the load when the conical rotor penetrated 20 mm from the surface of the toner powder phase at the time of penetration. The toner was brought into a compacted state in advance, the porosity was measured, and the torque and load were evaluated. The evaluation conditions for the conical rotor were as follows.
・ Consolidation load: 250g
・ Vertical angle of conical rotor: 50 °
・ Number of rotations of conical rotor: 1 rpm
-Penetration speed of conical rotor: 5 mm / min
All parts in the following formulations are parts by weight.
[0095]
Example 1
Resin: 100 parts of polyester resin
Pigment: (TiO) .Fe₂O 330 parts
Charge control agent: zinc salicylate 5 parts
Release agent: 5 parts of low molecular weight polyethylene
After sufficiently mixing the above raw materials with a mixer, the mixture was melt-kneaded with a twin-screw extruder at a barrel temperature of 100 ° C. and a kneader rotation speed of 120 rpm. The kneaded product was rolled and cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having an average particle size of 6.5 μm using a revolving air classifier.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0096]
Example 2
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 1, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0097]
Example 3
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 1, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0098]
Example 4
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 1, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0099]
Comparative Example 1
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 1, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0100]

After sufficiently mixing the above raw materials with a mixer, the mixture was melt-kneaded with a twin-screw extruder at a barrel temperature of 100 ° C. and a rotation speed of 120 rpm. The kneaded product was rolled and cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having an average particle size of 6.5 μm using a revolving air classifier.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0101]
Example 6
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 5, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0102]
Example 7
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 5, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0103]
Example 8
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 5, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0104]
Comparative Example 2
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 5, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.
Additive: silica fine powder 1.0 part
Mixing speed 700rpm
Mixing time 120 sec
Mixer Super Mixer
After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0105]
Example 9
Resin: 100 parts of polyester resin
Pigment: (GdO) .Fe₂O₃                              40 parts
Charge control agent: zinc salicylate 5 parts
Release agent: 5 parts of low molecular weight polyethylene
After sufficiently mixing the above raw materials with a mixer, the mixture was melt-kneaded by a twin-screw extruder at a barrel temperature of 100 ° C. and a kneader rotation speed of 120 rpm. The kneaded product was rolled and cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and then classified into a particle size distribution having an average particle size of 6.5 μm using a revolving air classifier.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. The results are shown in Table 1.
[0106]
Example 10
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 9, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0107]
Example 11
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 9, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0108]
Comparative Example 3
Kneading, pulverization, and classification were performed using the same raw materials and production method as in Example 9, and the particles were classified into a particle size distribution having an average particle size of 6.5 μm.
Further, an additive was mixed with 100 parts of the base colored particles under the following mixing conditions to prepare a toner.

After preparing the toner, the fluidity was measured by the evaluation method. Table 1 shows the results.
The obtained toner was set in a copying machine in which the latent image carrier was an OPC drum photosensitive member and the cleaning method was blade cleaning, and an image evaluation experiment and a running experiment were performed. Table 1 shows the results.
[0109]
[Table 1]

[0110]
The above data is graphed and shown in FIGS. FIG. 6 shows the relationship between the torque and the dot reproducibility when the conical rotor enters Examples 1 to 11 and Comparative Examples 1 to 3, and FIG. 7 shows the load when the conical rotor enters the Examples 1 to 11 and Comparative Examples 1 to 3. And the relationship between dot and dot reproducibility.
[0111]
As can be seen from the above results, there is a strong correlation between the fluidity evaluation value of the toner powder phase according to the evaluation method of the present invention and the image density, dot reproducibility and toner transportability. It can be seen that the image quality and toner transportability can be evaluated by the method. From the results of FIGS. 6 and 7, it is understood that the following conditions must be satisfied in order to obtain a toner having good fluidity, which is necessary for obtaining high image quality with good dot reproducibility.
{Circle around (1)} The value of the torque when the conical rotor enters is 0.1 to 1.9 mNm.
{Circle around (2)} The value of the load when the conical rotor enters is 0.01 to 0.37N.
(Here, rotor penetration speed: 5 mm / min, value at 20 mm penetration)
If the torque value at the time of entering the conical rotor is less than 0.1 mNm, the charging characteristics other than the fluidity of the toner are deteriorated, and the image quality is deteriorated. Reproducibility and toner transportability deteriorate. If the load value at the time of entering the conical rotor is less than 0.01 N, the charging characteristics of the toner deteriorate and the image quality deteriorates. If the load value exceeds 0.37 N, the fluidity of the toner decreases, the image density decreases, and the dot reproducibility and Poor toner transportability.
[0112]
【The invention's effect】
According to the present invention, at least the fluidity of a base toner powder composed of a pigment and a resin using a metal oxide, after the powder is preliminarily compacted, penetrate into the powder phase while rotating a conical rotor, By specifying the torque or load generated when the conical rotor penetrates into the powder phase, human-friendly electrostatic charge images with good toner transportability, high image density, high dot reproducibility, and high image quality can be obtained. The developing toner can be stably provided.
Further, according to the present invention, it is possible to provide a method for evaluating the toner, a developing method using the toner, a toner cartridge filled with the toner, a method for manufacturing the toner, and an evaluation device.
[Brief description of the drawings]
FIG. 1 is a schematic diagram of an evaluation device configuration of the present invention.
FIG. 2A is a diagram illustrating an example of the shape of a conical rotor.
(B) is a sectional view of (a).
FIG. 3A is a view of the conical roller as viewed from above.
(B) is the figure seen from the top of another example of the conical roller.
(C) is the figure seen from the side of the conical rotor.
FIG. 4 is a schematic view of a toner manufacturing apparatus provided with the evaluation device of the present invention.
FIG. 5 is a schematic diagram of a developing device using the electrostatic image developing toner of the present invention.
FIG. 6 is a diagram illustrating the relationship between the torque and the dot reproducibility when the conical rotor enters in Examples 1 to 11 and Comparative Examples 1 to 3.
FIG. 7 is a diagram illustrating a relationship between a load at the time of intrusion of a conical rotor and dot reproducibility in Examples 1 to 11 and Comparative Examples 1 to 3.

Claims (25)

An additive is adhered or fixed to the surface of a base toner powder composed of at least a pigment and a resin using a metal oxide, and the powder is preliminarily compacted. The value of the torque generated when entering the 20 mm powder phase is 0.1 to 1.9 mNm, or the value of the load generated when entering the 20 mm powder phase is 0.01 to 0.37 N. A toner for developing an electrostatic image, wherein The toner according to claim 1, wherein the metal oxide comprises an Fe oxide and a Ti oxide. 3. The electrostatic image developing toner according to claim 1, wherein the porosity of the powder phase in the compacted state is 0.50 to 0.64. The electrostatic image developing toner according to any one of claims 1 to 3, wherein at least one of the resins is a crystalline polyester represented by the following general formula (1).
_{[-O-CO-CR 1 =} CR 2 -CO-O- (CH 2) n -] m (1)
(In the formula, R ₁ and R ₂ represent a hydrocarbon group, and n and m represent the number of repeating units.) 5. The toner according to claim 1, wherein the metal oxide has an average particle size of 0.01 to 0.2 [mu] m. The toner according to claim 1, wherein the content of the metal oxide is 20 to 100 parts by weight based on 100 parts by weight of the resin. The electrostatic charge according to any one of claims 1 to 6, wherein a charge control agent and / or a release agent is contained in the base toner powder composed of a pigment and a resin using at least a metal oxide. Image developing toner. The electrostatic image developing toner according to claim 7, wherein a dispersant of a release agent is contained in the powder composed of the pigment, resin, and release agent using at least a metal oxide. 9. The electrostatic image developing toner according to claim 7, wherein a pulverization aid is contained in the powder comprising at least a pigment using a metal oxide, a resin, and a release agent. 10. The additive according to claim 1, wherein the additive adhered or fixed to the surface of the base toner powder comprising a pigment and a resin using at least a metal oxide is an inorganic fine powder having an average particle diameter of 10 to 200 nm. The toner for developing an electrostatic image according to any one of the above. 10. The additive according to claim 1, wherein the additive adhered or fixed to the surface of the base toner powder comprising a pigment and a resin using at least a metal oxide comprises a charge control agent having an average particle diameter of 10 to 200 nm. The toner for developing an electrostatic image according to any one of the above. The electrostatic image developing toner according to claim 1, wherein the toner is prepared using a composition in which a resin and a pigment are kneaded in advance. The electrostatic image according to claim 1, wherein an average circularity of the base toner powder including the pigment and the resin using at least the metal oxide is 0.90 to 0.99. Development toner. The electrostatic image developing toner according to claim 1, wherein the toner has a volume average particle diameter of 4 to 10 μm. A method for evaluating a toner in which an additive is attached or fixed to the surface of a base toner powder composed of a pigment and a resin using at least a metal oxide, wherein the additive is attached or fixed to the surface of the base toner powder. The toner powder is brought into a compacted state, and then, while rotating the cone rotor at a rotation speed of 0.1 to 100 rpm, the toner powder is caused to penetrate into the powder phase at a penetration speed of 0.5 to 150 mm / min. Alternatively, a method for evaluating a toner for developing an electrostatic image, comprising measuring a load. The method for evaluating a toner for developing an electrostatic image according to claim 15, wherein the conical rotor has an apex angle of 20 to 150 °. 17. The method according to claim 15, wherein a groove is formed in a surface of the conical rotor. 18. The method according to claim 15, wherein a rotation speed of the conical rotor is 0.1 to 10 rpm. A one-component developing method, wherein contact or non-contact development is performed using the electrostatic image developing toner according to claim 1. 20. The one-component developing method according to claim 19, wherein a doctor roller and / or a supply roller are used. A two-component developing method, comprising developing using the toner for developing an electrostatic image according to any one of claims 1 to 14 and a carrier having a particle size of 20 to 100 µm. 22. The developing method according to claim 19, wherein the developing is performed by applying an AC bias voltage component. A toner cartridge filled with the toner for developing an electrostatic charge image according to claim 1. 19. A method for producing a toner for developing an electrostatic charge image, comprising: evaluating the toner by the evaluation method according to claim 15; and selecting the toner so as to satisfy the conditions described in claim 1. 19. The apparatus according to claim 15, further comprising at least a toner container for developing an electrostatic image, a conical rotor, an elevator for injecting the conical rotor into the container, a torque meter and / or a load cell for measuring a load. A toner evaluation device for developing an electrostatic image, wherein the toner evaluation device evaluates the fluidity of the toner using the evaluation method described in (1) or (2).

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